Nonwoven composites and related products and methods

ABSTRACT

A method of forming a porous honeycomb substrate including a non-woven fibrous ceramic body is provided herein. The fibrous ceramic body is substantially composed of intertangled ceramic fiber forming a rigid three-dimensional matrix. Washcoat and catalyst materials can be applied to at least partially coat the honeycomb channels. The porous honeycomb substrate provides an improved substrate for use in filtration applications such as exhaust particulate filtration of internal combustion engines.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application includes material which is subject to copyrightprotection. The copyright owner has no objection to the facsimilereproduction of the patent disclosure, as it appears in the UnitedStates Patent and Trademark Office files or records, but otherwisereserves all rights. This application is a continuation of U.S. patentapplication Ser. No. 10/833,298 filed Apr. 28, 2004, which is acontinuation-in-part of U.S. patent application Ser. No. 10/281,179, nowU.S. Pat. No. 6,946,013, filed Oct. 28, 2002, which are bothincorporated by reference in its respective entirety.

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates to substrates useful for catalyzing particularreactions and for filtering particulate matter, and to embodimentsrelated thereto, such as but not limited to the treatment of emissionsfrom internal combustion engines, and more specifically tocatalyst/substrate combinations useful in emissions control and relatedprocesses and to related products and methods of manufacture. It isbelieved that embodiments of the invention described herein materiallyenhances the quality of the environment of mankind by contributing tothe restoration or maintenance of one or more basic life-sustainingnatural elements, including air, water, and/or soil. The invention andembodiments thereof are more fully described below in the Brief Summaryof the Invention and Detailed Description sections.

Exhaust, Industry, and Pollution

Engines produce much of the power and mechanical work used across theglobe. The internal combustion engine is perhaps the most widespreaddevice, as it is more efficient than an external combustion engine, suchas those that existed on old-fashioned trains and steamboats. Withinternal combustion engines, combustion of the fuel takes placeinternally. Such engines produce motion and power used for any number ofpurposes. Examples include motor vehicles, locomotives, marineapplications, recreational vehicles, tractors, construction equipment,generators, power plants, manufacturing facilities, and industrialequipment. Fuels used to power internal combustion engines include, butare not limited to gasoline, compressed gas, diesel, ethanol, andvegetable oil. Inherent inefficiencies in engine mechanics and the fuelsused to power the them result in emissions of various pollutants. Thus,while they are a great innovation and convenience, the millions ofengines used throughout the world today represent a substantial sourceof air pollution.

There are two main types of pollutants produced by internal combustionengines: particulate and nonparticulate. Particulate pollution isgenerally small solids and liquid particles. Examples includecarbonaceous soot and ash, dust, and other related particles.Nonparticulate pollutants include gases and small molecules, such ascarbon monoxide, nitrogen oxides, sulfur oxides, unburned hydrocarbons,and volatile organic compounds. Particulate pollutants can be filteredfrom the exhaust and, in certain situations, further burned off.Nonparticulate pollutants are converted to nonpollutants. Both kinds ofpollutants can also be produced from non-engine sources, such as“off-gas” chemical reactions and evaporative emissions.

Air pollution can cause serious health problems for people and theenvironment. Ground-level ozone and airborne particles are the twopollutants that pose one of the greatest threats to human health in thiscountry. Ozone (O₃), can irritate the respiratory system, causingcoughing, irritation in the throat, and/or a burning sensation in therespiratory airways. Ozone contributes to the formation of smog. Ozonecan also reduce lung function, causing feelings of chest tightness,wheezing and shortness of breath, and can aggravate asthma. Particlepollution, is composed of microscopic solids or liquid droplets that aresmall enough to get deep into the lungs and cause serious healthproblems. When exposed to these small particles, people may experiencenose and throat irritation, lung damage and bronchitis, and can increasetheir risk of heart or lung disease. Short-term effects of airpollutants include irritation to the eyes, nose, and throat. Upperrespiratory infections such as bronchitis and pneumonia may also result.Other symptoms can include headaches, nausea, and allergic reactions.Long-term health effects can include chronic respiratory disease, lungcancer, heart disease, and even damage to the brain, nerves, liver, orkidneys. Continual exposure to air pollution affects the lungs ofgrowing children and may aggravate or complicate medical conditions inthe elderly.

Medical conditions arising from air pollution can be very expensive.Healthcare costs, lost productivity in the workplace, and human welfareimpacts cost billions of dollars each year. Understanding the healtheffects of pollution and finding means to ameliorate, prevent, oreliminate pollution would not only enhance the overall respiratoryhealth of the population but would also decrease the substantial burdenand cost borne by the healthcare system.

For all of these reasons, governments, environmental agencies, andvarious industries have committed to reducing the level of air pollutionemitted from various sources. Government agencies are the principalbodies setting emissions standards and implementing regulations. In theEuropean Union (EU), regulations stem from European Communitylegislation; individual countries enforce the regulations. For instance,most EU states have taxes on sources that produce excessive airpollution. A recent development was the Kyoto Protocol, which called forworldwide reductions in greenhouse gases. Many nations, including theEU, ratified the protocol. The EU, Japan, and U.S. have enacted some ofthe most stringent standards worldwide, but many other countries,including Argentina, Brazil, Mexico, Korea, Thailand, India, Singapore,and Australia, have all enacted regulations on air pollution. In theU.S., there are many different groups that affect regulations in certaingeographies, such as: state environmental agencies (e.g., California AirResources Board (CARB)), national parks, forest agencies, and the MineSafety and Health Administration. Some states and metropolitan areasthat have failed national ambient air quality standards (NAAQS) havebeen designated as “non-attainment areas” and implement standards oftheir own. CARB has historically been one of the strictest agenciesregulating air pollution in the U.S. The chief U.S. regulatory agency,however, is the Environmental Protection Agency (EPA). It was created bythe Nixon administration in the 1970 amendments to the Clean Air Act(CAA) of 1963. The Clean Air Act is the comprehensive Federal law thatregulates air emissions from area, stationary, and mobile sources. (See,e.g., 42 U.S.C. SS 7401 et seq. (1970) of the Clean Air Act). The CleanAir Act has had five major amendments, the most recent of which was in1990. The 1990 amendments to the Clean Air Act in large part wereintended to meet unaddressed or insufficiently addressed problems suchas acid rain, ground-level ozone, stratospheric ozone depletion, and airtoxics. These amendments required the EPA to issue 175 new regulations,including automotive emissions, gasoline reformation, uses of ozonedepleting chemicals, etc.

Following the Clean Air Act legislation, the EPA set regulations forpollutants that are or could be harmful to people. This set of “criteriapollutants” includes: (1) ozone (O₃); (2) lead (Pb); (3) nitrogendioxide (NO₂); (4) carbon monoxide (CO); (5) particulate matter (PM);and (6) sulfur dioxide (SO₂). Each criteria pollutant is described inturn.

Ground-level ozone (a primary constituent of smog) continues to be apollution problem in the U.S. Ozone is not emitted directly into the airbut is formed by the reaction of volatile organic compounds (VOCs) orreactive organic gases (ROGs) and nitrogen oxides (NOx) in the presenceof heat and sunlight. VOCs/ROGs are emitted from a various sourcesincluding burning fuels, and from solvents, petroleum processing, andpesticides, which come from sources such as motor vehicles, chemicalplants, refineries, factories, consumer and commercial products, andother industrial sources. Nitrogen oxides are emitted from motorvehicles, power plants, and other sources of combustion. Ozone and theprecursor pollutants that cause ozone also can be carried miles fromtheir original sources by wind. In 1997, the EPA revised the nationalambient air quality standards for ozone by replacing the 1-hour ozone0.12 parts per million (ppm) standard with a new 8-hour 0.08 ppmstandard.

Nitrogen dioxide (NO₂) is a reactive gas that can be formed by theoxidation of nitric oxide (NO). Nitrogen oxides (NOx), the term used todescribe NO, NO₂, and other oxides of nitrogen, play a major role in theformation of ozone and smog. The major sources of man-made NOx emissionsinclude high-temperature combustion processes, such as those occurringin automobiles, heavy construction equipment, and power plants. Homeheaters and gas stoves also produce substantial amounts of NO₂.

Carbon monoxide (CO) is a colorless, odorless, and poisonous gas thatcan be formed by incomplete combustion of carbon in fuels. Motor vehicleexhaust contributes about 60% of CO emissions in the U.S. In cities, asmuch as 95% of CO emissions may come from automobile exhaust. Othersources of CO emissions include industrial processes, non-transportationfuel combustion, and natural sources such as wildfires.

Particulate matter (PM) is a term used for a mixture of solid particlesand liquid droplets found in the air. Some particles are large or darkenough to be seen as soot or smoke. Others are so small they can bedetected only with an electron microscope. These particles, which comein a wide range of sizes (“fine” particles are less than 2.5 micrometersin diameter and coarser particles are larger than 2.5 micrometers),originate from many different stationary and mobile sources as well asfrom natural sources. Fine particles (PM-2.5) result from fuelcombustion from motor vehicles, power generation, and industrialfacilities, as well as from residential fireplaces and wood stoves.Coarse particles (PM-10) are generally emitted from sources such asvehicles traveling on unpaved roads, materials handling equipment, andcrushing and grinding operations, as well as windblown dust. Someparticles are emitted directly from their sources, such as smokestacksand cars. In other cases, gases such as sulfur oxide, SO₂, NOx, and VOCinteract with other compounds in the air to form fine particles. Theirchemical and physical compositions vary depending on location, time ofyear, and weather. In 1997, the EPA added two new PM-2.5 standards, setat 15 micrograms per cubic meter (μGA) and 65 μg/m³, respectively, forthe annual and 24-hour standards.

Sulfur dioxide can be formed when fuel containing sulfur (such as coaland oil) is burned, for example, during metal smelting and otherindustrial processes.

The last criteria pollutant, lead, was historically produced from use ofleaded fuel in automobiles. As a result of regulatory efforts to reducethe content of Pb in gasoline, the contribution from the transportationsector has declined over the past decade. Today, metals processing isthe major source of Pb emissions to the atmosphere.

The Clean Air Act requires to EPA and states to develop plans to meetnational ambient air quality standards for these six criteriapollutants. Outside of the six is a separate list of 188 “toxic airpollutants.” Examples of toxic air pollutants include benzene, found ingasoline; perchloroethylene, emitted from some dry cleaning facilities;and methylene chloride, used as a solvent and paint stripper by a numberof industries. Some air toxics are released from natural sources, butmost originate from anthropogenic sources, including both mobile sources(e.g., cars, trucks, and buses) and stationary sources (e.g., factories,refineries, and power plants). The CAA required the EPA to have atwo-phased program for these 188 pollutants. The first phase consists ofidentifying the sources of toxic pollutants and developingtechnology-based standards to significantly reduce them. The EPAdetermined a list of over 900 stationary sources, which resulted in newair toxics emissions standards, affecting many industrial sources,including: chemical plants, oil refineries, aerospace manufacturers, andsteel mills, as well as smaller sources, such as dry cleaners,commercial sterilizers, secondary lead smelters, and chromiumelectroplating facilities. The second phase consists of strategies andprograms for evaluating the remaining risks and ensuring that theoverall program has achieved substantial reductions; this phase is stillin progress.

Internal combustion engines are directly affected by these regulationssince they emit criteria pollutants. These engines run on two fuel. Themost common types of fuel used are: gasoline and diesel. Each type offuel contains complex mixtures of hydrocarbon compounds as well astraces of many other materials, including sulfur. Even when burnedcompletely, these fuels produce pollutants. Moreover, because no engineis capable of “perfect” combustion, some fuel is incompletely oxidizedand therefore produces additional pollutants. Other types of fuel canalso be used, for example, ethanol mixtures, vegetable oils, and otherfuels known in the art.

In gasoline engines, in order to reduce emissions, modern car enginescarefully control the amount of fuel they burn. They try to keep theair-to-fuel ratio very close to the stoichiometric point, which is thecalculated ideal ratio of air to fuel. Theoretically, at this ratio, allof the fuel will be burned using all of the oxygen in the air. The fuelmixture actually varies from the ideal ratio quite a bit during driving.Sometimes the mixture can be lean (e.g., an air-to-fuel ratio higherthan the typical value of 14.7), and other times the mixture can be rich(e.g., an air-to-fuel ratio lower than 14.7). These deviations result invarious air emissions.

Significant emissions of a gasoline car engine include: nitrogen gas(N₂) (air is 78% N₂); carbon dioxide (CO₂), a combustion product; andwater vapor (H₂O), another combustion product. These emissions aremostly benign to humans (although excess levels of atmospheric CO₂ arebelieved to contribute to global warming). Gasoline engines, however,also produce carbon monoxide, nitrogen oxides, and unburnedhydrocarbons, all of which are included in the EPA's criteria pollutants(unburned hydrocarbons form part of the ozone formation mechanism, alongwith NOx).

Diesel engines also contribute to the criteria pollutants. These enginesuse hydrocarbon fractions that auto-ignite when compressed sufficientlyin the presence of oxygen. In general, diesel combusting within acylinder produce greater amounts of particulate matter and thepollutants nitrogen and sulfur oxides (NO_(x) and SO_(x) respectively)than does gasoline. Even so, diesel mixtures are generally lean, withrelatively abundant amounts of oxygen present. Consequently, thecombustion of smaller hydrocarbons is usually more complete, producingless carbon monoxide than gasoline. Longer chain hydrocarbons are moredifficult to burn completely and can result in the formation ofparticulate residues such as carbon “soot.”

Despite these drawbacks, fossil fuels are relatively abundant, easy tohandle, and economical. Thus, these fuels will continue to represent asignificant source of mechanical power and pollution for years to come.Moreover, the pervasiveness of the internal combustion engine indicateshow fossil fuels will continue to be a necessary source of energy.

There are at least three markets of internal combustion engines thatproduce air significant pollution: 1) mobile, on-road engines,equipment, and vehicles 2) mobile, non-road engines, equipment, andvehicles and 3) stationary or “point” sources. In each of these markets,government agencies and other organizations have dictated restrictionson levels of air pollution. These restrictions have become increasinglystringent as the number of internal combustion engines in useproliferates and more is learned about the harm caused by air pollution.The ever-tightening regulations have required industries to continuouslyresearch, develop, and invest in new emissions control technologies,from fuel formulations to engine redesign, to after treatment devices.These technologies vary in both effectiveness and cost but have becomeessential in order for companies to comply with regulations. No singleemissions control technology has been able to remove all relevantpollutants, so multiple technologies often have to be used together inorder to enable a particular type of vehicle or equipment to meetregulatory emission limits. These markets, their regulations, and thetechnologies on which they rely are described in the followingparagraphs. The technologies, including their benefits and drawbacks,are described in more detail following this section. While the sectionsfocus on U.S. engines, equipment, and vehicles, other geographies havesimilar products and regulations. For instance, the EU has similarmarket sizes but focuses more on selective catalytic reduction thanexhaust gas recirculation as a diesel emission control technology, usescatalytic converters in a greater percentage of its small, off-roadengines, and has a much larger percentage of diesel engines in lightduty vehicles. Other geographies have their own characteristicdifferences from the U.S., but essentially use the same types ofequipment and restrict the same types of air pollutants.

The mobile, on-road engines, equipment, and vehicles include, but arenot limited to, passenger cars, pickup trucks, minivans, sport-utilityvehicles (SUVs), buses, delivery trucks, semi-trucks, passenger vans,and two or three-wheeled motorcycles designed for on-road use. Thesemarkets historically have lead the way in emissions control and continueto do so today by following regulations that dictate lower levels of airpollutants.

The car and truck markets are divided by weights. Those under 8,500pounds Gross Vehicle Weight Rating (GVWR) are considered light dutyvehicles. Vehicles between 8,500 and 10,000 lbs GVWR that are designedfor passenger transport are considered medium duty vehicles. Vehiclesover 8,500 lbs GVWR that are not designed for personal use are labeledas heavy-duty vehicles.

Passenger cars and light-duty vehicles were previously regulated byvehicle weight and fuel type but will be regulated in one group infuture standards. Less than 1% of ˜17 million new passenger cars andlight-duty vehicles produced in the United States use diesel engines.Passenger cars and light-duty vehicles includes those made bymanufacturers such as Ford, General Motors (GM), DaimlerChrysler, BMW,Honda, Hyundai, Daewoo, First Automobile Group, Toyota, Nissan,SAIC-Chevy and Subaru.

Regulations on passenger cars and light-duty vehicles have existed fordecades but have recently become much more stringent. The Tier 2standards, phasing in from model year (MY) 2004-2009, require originalequipment manufacturers (OEMs) to certify their fleet into certain“bins” of standards and to maintain a corporate average for NOxemissions. Vehicles under 6,000 lbs GVWR must be fully compliant by2007, those from 6,000-8,500 lbs and MDVs must be compliant by 2009.Pollutants included in the standards include: NOx, formaldehyde (HCHO),CO, PM, and non-methane organic gases. California has historically hadtighter regulations than the EPA, and other states, including NewJersey, New York, Vermont, Maine, and Massachusetts, have joined inCalifornia's even lower emissions levels for new and used vehicles.Manufacturers who do not meet the standards are essentially prohibitedfrom producing their vehicles in these markets, and are fined for onesdiscovered on the market. In the aftermarket, states regulate cars andlight duty vehicles' emissions through inspection and maintenance (I/M)programs. These programs are often created from state implementationplans (SIPs) required in national ambient air quality (NAAQ)non-attainment areas. Meeting both new vehicle and aftermarket standardsrequires the use of emission control technologies, often in parallel.

Historically, three-way catalytic converters have had widespread use incars and light-duty vehicles. Recent improvements in these converters(such as increased substrate porosity, an optimized washcoat, reducedcatalyst loading, etc), have yielded incremental improvements inemissions control. To meet the newest set of U.S. regulations,manufacturers will likely increase catalyst loading or the number ofsubstrates per vehicle. Cars in use that do not meetinspection/maintenance standards have to replace the faulty technologyor purchase additional devices. Other emission control devices include,but are not limited to, advanced injection systems (such as injectiontiming, injection pressure, rate shaping, common rail injection, andelectronic controls), changed combustion chamber design (such as highercompression ratios, piston geometry, and injector location), variablevalve timing, catalytic converters, and filters.

Heavy-duty vehicles (HDV) include both private and commercial trucks andbuses over 8,500 lbs GVWR. The vast majority of these engines run ondiesel fuel; over 300,000 are produced each year in the U.S.Manufacturers and engine suppliers include, but are not limited to,Cummins, Caterpillar, Detroit Diesel, GM, Mack/Volvo,International/Navistar, Sterling, Western Star, Kenworth, and Peterbilt.Other companies offering other emission control technologies for theaftermarket include, but are not limited to, Donaldson, Engelhard,Johnson Matthey, Lubrizol, Fleetguard, Cleaire, Clean Air Partners, andEngine Control Systems.

Heavy-duty trucks are facing rigorous emissions-reducing standards forPM, NOx, CO, and non-methane hydrocarbons (NMHC). The PM standard takeseffect in 2007, while NOx and NMHC standards phase-in from 2007-2010.Similar to light duty vehicles, California, along with certain otherstates and metropolitan areas, has often enacted tighter emissionsstandards than the EPA. For vehicles that do not meet standards, themanufacturers are prohibited from selling them. Non-compliance penaltiesfor NOx range up to $12,000 per vehicle, based on size and complianceeffort. While other industries, such as locomotive, marine, agriculture,and construction use highly similar engines to those in heavy-dutyvehicles, the HDV market has faced the tightest emission standards.Meanwhile, some states and metropolitan areas (such as California, NewYork City, and Seattle) require additional retrofits or offer incentivesfor retrofits to further bring down pollution levels. These areas havecertified technologies that meet the approved levels and qualifications.Examples include Donaldson's diesel oxidation catalyst muffler anddiesel particulate filter, Cleaire's diesel oxidation catalyst anddiesel particulate filter, and Johnson Matthey's continuouslyregenerating technology particulate filter.

Emissions control technologies used to meet these standards and forretrofits include, but are not limited to, advanced injection systems(injection timing, injection pressure, rate shaping, common railinjection, electronic controls), exhaust gas recirculation, changes incombustion chamber design (higher compression ratios, piston geometry,and injector location), advanced turbocharging, ACERT, dieselparticulate filters, NOx adsorbers, selective catalytic reduction,conventional catalytic converters, catalytic exhaust mufflers, anddiesel oxidation catalysts. Meeting the 2007 standards has initiated newresearch and development on many of these emission control technologies.There has been tremendous cost and effort put into determining anemissions control solution for 2007 HDVs.

Motorcycles are another type of mobile, on-road vehicle and include bothtwo and three-wheeled motorcycles designed for on-road use. Motorcyclesprimarily use gasoline fuel. Manufacturers include, but are not limitedto: Harley Davidson, BMW, Honda, Kawasaki, Triumph, Tianjin Gangtian,Lifan Motorcycle, and Yamaha. Regulations for on-road motorcycles wereadopted in 1978 and then left unrevised through 2003, when new standardsfollowing those in California were agreed upon. Pollutants monitored inthe new standards include HC, NOx, and CO.

Emissions control technologies for motorcycles include, but are notlimited to, conversion of 2-stroke engines to 4-stroke, advancedinjection systems (injection timing, injection pressure, rate shaping,common rail injection, and electronic controls), pulse air systems,changed combustion chamber design (higher compression ratios, pistongeometry, and injector location), and use of catalytic converters.Limitations in motorcycles' emissions control technologies are differentthan those in light or heavy-duty vehicles. Motorcycles focus more onthe appearance, placement, and heat of aftertreatment devices, as thereare fewer places to “hide” the device and the passenger is in muchcloser proximity to the exothermic oxidation reaction.

The mobile, non-road engines, equipment, and vehicles category includes,but is not limited to, engines for agriculture, construction, mining,lawn and garden, personal watercraft, boats, commercial ships,locomotives, aircraft, snowmobiles, off-road motorcycles, and ATVs.

Small engines emit significant levels of air pollution for their size;they are the largest single contributor to nonroad HC inventories. Smallengine equipment includes, but is not limited to, leaf blowers,trimmers, brush cutters, chainsaws, lawn mowers, engine riding mowers,wood splitters, snowblowers, and chippers. Engine and equipmentmanufacturers include, but are not limited to, John Deere, Komatsu,Honda, Ryobi, Electrolux (Husqvarna and Poulan, also suppliesCraftsman), Fuji, Tecumseh, Stihl, American Yard Products, and Briggsand Stratton.

The EPA began regulating small engines in 1993 (Phase I) with standardsthat went into effect in 1997 and continued to reduce emission levelswith new standards in 2002 (Phase II). The standards divide theequipment into handheld and non-handheld categories and categorize itbased on different engine displacements. The regulations focus onhydrocarbons and nitrogen oxides emissions.

Emissions control technologies include, but are not limited to, use of acatalyst (i.e., John Deere's LE technology and Komatsu's “StratifiedScavenged” design), converting 2-stroke engines to 4-stroke, advancedinjection systems (injection timing, injection pressure, rate shaping,common rail injection, electronic controls), or changing combustionchamber design (higher compression ratios, piston geometry, and injectorlocation).

The recreational vehicle markets include off-highway motorcycles,snowmobiles, and all-terrain vehicles (ATVs). These are made bymanufacturers and engine suppliers such as: Caterpillar, Cummins,Detroit Diesel, Ford Power Products, GM, Honda, John Deere, Kawasaki,Mitsubishi Motors, Nissan, Toyota, Yanmar, Arctic Cat, Bombardier,Brunswisk, International Powercraft, Polaris, Suzuki, and Yamaha.

The EPA began regulating recreational vehicles later than many othermarkets, though California had regulations in place beforehand. EPA hasphase-ins from 2006-2009 for snowmobiles, and 2006-2007 for off-highwaymotorcycles and ATVs. The regulated pollutants include HC, CO, and NOx.Emission control technologies for recreational vehicles include, but arenot limited to, converting 2-stroke engines to 4-stroke, advancedinjection systems (injection timing, injection pressure, rate shaping,common rail injection, electronic controls), pulse air, or changingcombustion chamber design (higher compression ratios, piston geometry,and injector location).

In mining, regulations are established by the Mine Safety and HealthAdministration. Mining is often considered one of the most taxingenvironments for equipment, due to the high levels of vibration, impact,and dust. Temperature and flammability are also larger concerns inmining. Diesel oxidation catalyst have been retrofitted on some miningequipment, while diesel particulate filters are becoming more common.

In the agriculture and construction markets, the EPA regulates bothspark-ignition and compression-ignition engines. These can be used intractors, forklifts, bulldozers, electric generators, pavers, rollers,trenchers, drill rigs, mixers, cranes, balers, compressors, etc.Manufacturers of engines and equipment include, but are not limited to:Agco, Komatsu, CNH Global, Caterpillar, Cummins, Daewoo, John Deere &Co, Dueutz, Detroit Diesel, and Kubota.

The EPA began regulating the diesel portion of these engines in 1994(Tier 1) and has more recently increased the standards with Tier 2(phased in from 2001-2006). The standards are slated to increase againwith Tier 3 levels from 2006-2008. The Tier 3 levels will likely requirethe use of emissions control devices similar to those used on heavy-dutyvehicles (such as tractor-trailers). The gasoline, liquid propane gas,or compressed natural gas (CNG) engines used in agriculture andconstruction applications have also had recent changes in regulations.Tier 1 levels began in 2004 and match those adopted earlier by CARB;Tier 2 levels are expected to start in 2007. A voluntary program forvehicles with lower emissions than the standards exists, named “BlueSkies Series.” Based on engine size and fuel type, the levels ofparticulates, carbon monoxide, nitrogen oxides, and non-methanehydrocarbons all must be significantly reduced for current phase-ins andfor shortly forthcoming standards.

Emissions control technologies are similar to those used on heavy-dutyvehicles and includes, but is not limited to, advanced injection systems(injection timing, injection pressure, rate shaping, common railinjection, electronic controls), exhaust gas recirculation, changes incombustion chamber design (higher compression ratios, piston geometry,and injector location), advanced turbocharging, ACERT, dieselparticulate filters, NOx adsorbers, selective catalytic reduction,conventional catalytic converters, catalytic exhaust mufflers, anddiesel oxidation catalysts. Exhaust gas recirculation (EGR) has beenproblematic due to its tendency to create sulfuric acid formation in theengine's intake. It also requires cooling, which necessitates a largerradiator, and thus a larger nose on the vehicle, creating aerodynamicand fuel economy constraints.

In marine applications, engines can generally be divided by use ofgasoline or diesel fuel, personal or commercial use, or by engine size.Marine units range from personal watercraft, to yachts, to ferries, totugs and ocean-going ships. Manufacturers and engine suppliers include,but are not limited to: Bombardier (Evinrude, Johnson, Ski Doo, Rotax,etc), Caterpillar, Cummins, Detroit Diesel, GM, Isuzu, Yanmar, AlaskaDiesel, Daytona Marine, Marine Power, Atlantic Marine, BenderShipbuilding, Bollinger Shipyards, VT Halter Marine, EasternShipbuilding, Gladding-Hearn, JeffBoat, Main Iron Works, Master Boat,Patti Shipyard, Quality shipyards, and Verret Shipyard, MAN B&W Diesel,Wartsila, Mitsubishi, Bath Iron Works, Electric Boat, Northrop Grumman(includes Avondale, Ingalls, and Newport News Shipyards).

The EPA regulates boats whether they are recreational, private, orcommercial. The major category divisions are based on enginedisplacement, from recreational vehicles to tankers. Diesel marinenon-recreational boats under thirty liter (30 L) displacement, includingfishing boats, tugboats, towboats, dredgers, and cargo vessels, have newstandards for NOx and PM going into effect between 2004 and 2007,depending on engine size. Diesel marine non-recreational boats over 30L, including container ships, tankers, bulk carriers, and cruise ships,have NOx standards going into effect in 2004 (Tier 1) and additional HC,PM, and CO standards in 2007 (Tier 2). Diesel marine recreational boats,including yachts, cruisers, and other types of pleasure craft, havestandards matching those of diesel marine non-recreational boats under30 L displacement, but have later implementation dates, ranging from2006-2009 based on engine size. Gasoline and diesel boats only haveregulations currently applying HC emissions in outboard engines,personal watercraft, and jetboats. Sterndrive and inboard engines areinherently cleaner and are not yet regulated.

Emissions control technologies are similar to those used on heavy-dutyvehicles and include, but are not limited to, using “green terminals”when the boat is at dock, conversion from 2-stroke to 4-stroke engines,water aftercooling, exhaust gas recirculation, diesel particulatefilters, selective catalytic reduction, diesel oxidation catalyst,catalytic converters, advanced fuel injection (injection timing,injection pressure, rate shaping, common rail injection, electroniccontrols), advanced turbocharging, variable valve timing, and changingthe combustion chamber design (higher compression ratios, pistongeometry, and injector location). Using smaller engines for auxiliarypower (e.g., auxiliary power unit, APU) also helps to control emissions.While salt water and its associated pollutants and cooling effect onboats present difficulties in aftertreatment, the APU may work well withan aftertreatment device.

The locomotive market relies principally on diesel fuel (coal andwood-fired have limited use) and includes trains used in freight andpassenger rail, line-haul, local, and switch yard service. There areover 600 trains produced each year in the U.S. Manufacturers and enginesuppliers include, but are not limited to, GM's Electromotive Division,GE Transportation Systems, Caterpillar, Detroit Diesel, Cummins,MotovePower, Peoria Locomotive Works, Republic Locomotives, Trinity,Greenbrier, and CSX.

Regulations on trains began in 2000 and largely imitated those ofheavy-duty vehicles. The standards include levels for newly producedengines, as well as for engines that are remanufactured (which occursapproximately ever 4-8 years) and vary based on whether the engine isfor switch or line-haul purposes. Tier 0 applies to engine model years(MY) from 1973-2001, Tier 1 to MY2002-2004, and Tier 2 to MY2005 andlater. A non-compliance penalty can range up to $25,000 per engine perday. The pollutants regulated include particulate matter, NOx, HC, CO,and smoke opacity.

Emissions control technologies are similar to those used on heavy-dutyvehicles and include, but are not limited to, advanced injection systems(injection timing, injection pressure, rate shaping, common railinjection, electronic controls), exhaust gas recirculation, changes tocombustion chamber design (higher compression ratios, piston geometry,and injector location), selective catalytic reduction, diesel oxidationcatalysts, and aftercoolers, split cooling, zeolite sieves, and NOxreduction catalysts. Using a smaller, auxiliary power unit is alsobecoming an emissions control strategy, one which has fewer restrictionsaround the use of an aftertreatment device

The aircraft market includes all types of aircraft, including planesmade by Boeing, Airbus, Cessna, Gulfstream, and Lockheed Martin, amongothers. Both the EPA and European Union follow the International CivilAviation Organization's (ICAO) emissions standards. The EPA adoptedICAO's current standards for CO and NOx in gas turbine engines in 1997,having adopted their HC levels in 1984. In the U.S., the FAA monitorsand enforces these standards. Much of the emissions control is donethrough engine technologies and fuel changes.

Stationary sources include those sources of pollution that arenon-mobile. The EPA has issued rules covering over 80 categories ofmajor industrial sources, including power plants, chemical plants, oilrefineries, aerospace manufacturers, and steel mills, as well ascategories of smaller sources, such as dry cleaners, commercialsterilizers, secondary lead smelters, and chromium electroplatingfacilities. Power plants can use stationary diesel engines, stationarygas turbines, and nuclear power, among other sources. Each of thesesources produces different pollutants; for instance, nuclear powerplants produce iodine and hydrogen, gas turbines produce NOx, CO, SOx,CH4, and VOCs, and refineries produce gaseous vapors, CO, NOx, VOCs,CO2, CH4, and PM. Each industry requires different control technologiesto reduce air emissions.

EPA regulations cover the six criteria pollutants and the additional 188toxic air pollutants. Specific programs implemented include the AcidRain Program, designed to reduce sulfur emissions and the OzoneTransport Commission's NOx Budget Program, designed to reduce NOxemissions. RECLAIM is a program established for trading NOx and SOxcredits. In addition, cap and trade programs have been implemented insome industries and geographies, allowing companies to trade theiremission credits.

The technology used to control emissions from stationary sources varieswidely, but examples include filters, scrubbers, sorbents, selectivecatalytic reduction (SCR), precipitators, zero-slip catalysts, catalystsfor turbines, or oxidation catalysts. Some of the suppliers of emissionscontrol systems to stationary markets include: M+W Zander, Crystall,Jacobs E., Takasogo, IDC, ADP, Marshall, Bechtel, Megte, Angui, Adwest,Eisenmann, Catalytic Products, LTG, Durr, Siemens, Alston. Catalystsuppliers include: Nikki, BASF, Cormetech, W.R. Grace, Johnson Matthey,UOP, and Sud Chemie.

Due to the importance of improving air quality and complying withrelevant laws and regulations, substantial time, money, and effort havebeen invested in technologies capable of reducing emissions. Threegeneral areas of technology include, a) engine improvements, b) fuelimprovements, and c) after-treatments. These approaches are typicallynot mutually exclusive or stand-alone solutions. Engine improvementsinclude, but are not limited to, such technologies as: advancedinjection systems, exhaust gas recirculation, electronic sensors andfuel controls, combustion chamber designs, advanced turbocharging, andvariable valve timing. Fuel improvements include, but are not limitedto, such formulations as: high cetane, low aromatics, low sulfur fuel,fuel borne catalysts, liquefied petroleum gas (LPG), oxygenation offuels, compressed natural gas (CNG) and biodiesels. After-treatmenttechnologies include, but are not limited to: catalytic converters (2,3, and 4-way), particulate traps, selective catalytic reduction, NOxadsorbers, HC adsorbers, NOx reduction catalysts, and many others. Somesystems incorporate various pieces of these and other technologies;ACERT by Caterpillar or catalyzed diesel particulate traps are examplesof combination systems and devices. There are also some technologiesthat are currently limited in use, either by technological or commercialrestrictions.

Advanced injection systems include changes in injection timing,injection pressure, rate shaping, air-assisted fuel injection,sequential multi-point injection, common rail injection, resizing ormoving the injector holes, and some electronic controls. In thecommon-rail system, a microcomputerized fuel pump controls the flow andtiming of fuel (e.g., the Mercedes-Benz E320 uses this system).Secondary air injection can promote HC and CO combustion in themanifold. Changing the injection system can reduce a variety ofemissions and can also increase fuel economy; however, this requiressignificant work on the engine to ensure efficiency.

Exhaust gas recirculation (EGR) directs some of the exhaust gases backinto the intake of the engine. By mixing the exhaust gases with thefresh intake air, the amount of oxygen entering the engine is reduced,resulting in lower nitrogen oxide emissions. EGR does not requireregular maintenance and works well in combination with high swirl, highturbulence combustion chambers. EGR also has drawbacks, such as reducedfuel efficiency and engine life, greater demands on the vehicle'scooling system, limited to no effect on pollutants other than NOx, andit requires control algorithms and sensors. For these reasons, EGR isoften used in parallel with another control technology. Companiesinvolved in EGR technology include Doubletree Technologies, ETC, STTEmtec, Cummins, Detroit Diesel, Mack, and Volvo.

Optimizing the combustion chamber, or making incremental improvements toit, is another way manufacturers and developers are controllingemissions. Reducing the crevice volumes can limit trapping of unburnedfuel (and thus HC formation), while reducing the amount of lubricatingoil can also reduce HC formation and can limit catalyst poisoning. Othermeasures include: improving the surface finishes of cylinders andpistons, improving piston ring design and material, and improvingexhaust valve stem seals. Also, a “fast burn” combustion chamber can bemade by: increasing the rate of combustion, reducing the spark advance,adding a dilutent to the air-fuel mixture, and/or increasing turbulencein the chamber. While optimizing the combustion chamber can lead toreduced emissions, it is another technology that requires reworking ofthe engine, which can be an expensive process.

Variable valve timing involves calibrating the engine valves to open andclose for maximum fuel and engine efficiency. Often, a sensor is used todetect the engine's speed and to adjust the valve openings and closingsaccordingly. This technology can increase engine torque and horsepowerand can improve swirl and intake charge velocity, thus improving theefficiency of combustion. Variable valve technology does not reduceemissions as much as some other technologies and often leads toreductions in fuel efficiency.

Reformulating or using different fuels is another emissions controltechnique, as some fuels naturally pollute more than others, while sometend to poison the catalysts that would otherwise clean the exhaust air.For instance, the shift from leaded to unleaded fuel in the U.S. greatlydecreased lead emissions. Lowering the sulfur content in fuel reducesSOx emissions and increases the efficiency of many catalytic converters,as sulfur can poison catalysts. Another type of fuel, natural gas,typically produces less particulate pollution than diesel fuel and alsocan reduce NOx and combustion noise. Conversely, natural gas also canincrease vehicle weight (due to the need for high pressure tanks) andhas refueling limitations.

Using an aftertreatment device—equipment that is used after the fuel iscombusted—is very common in certain industries affected by emissionscontrol regulations. One example of an aftertreatment device is acatalytic converter. Catalytic converters can vary widely and can havedifferent functions, but the general description is a device that treatsexhaust with the use of catalysts. The composition of the substrates andthe catalysts that are on it have changed throughout the years, as hasthe placement and the number of converters.

A two-way catalytic converter performs oxidation of gas-phase pollution,such as the oxidation of HC and CO to CO₂ and H₂O. Diesel oxidationcatalysts (DOCs) are another type of two-way catalytic converter usedwith diesel engines. While these converters are effective at controllingHC and CO and require little maintenance, they can increase NOxemissions and are sensitive to sulfur.

A three-way catalytic converter performs both oxidation (conversion ofCO and HC to CO₂ and H₂O) and reduction (conversion of NOx to N₂ gas)reactions. Since the 1970s, three-way catalytic converters have reducedvehicle emissions. Further performance improvements by these devices arelimited by a number of factors, such as the temperature range andsurface area of their substrates and by catalyst poisoning. To meetincreasingly stringent regulations, some cars require multiple catalyticconverters.

A four-way catalytic converter performs oxidation and reductionreactions, and traps particulates to burn them off (regeneration canoccur in active or passive mode).

Suppliers of catalytic converters and their associated parts include,but are not limited to, Corning, NGK, Denso, Ibiden, Emitec, JohnsonMatthey, Engelhard, Catalytic Solutions, Delphi, Umicore, 3M,Schwäbische Hütten-Werke GmbH (SHW); Hermann J. Schulte (HJS), CleanDiesel Technology, Cleaire, Clean Air Systems, ArvinMeritor, Tenneco,Eberspacher, Faurecia, Donaldson, and Fleetguard.

Particulate traps or filters are another type of aftertreatment devicecommonly used in diesel applications, as diesel fuel generates moreparticulate matter than gasoline or some alternative fuels. In a dieselparticulate trap (DPT), particles in the exhaust stream pass through afilter that collects them. The removal of particulate matter that iscollected on the trap is referred to as “regeneration” and can occur inmultiple ways. One method uses external heaters to raise the temperatureof the filter to a level necessary for the PM to “burn off.” Anothermethod releases small amounts of diesel fuel in the exhaust stream. Whenthe fuel particles come in contact with the filter, the fuel burns offat an elevated temperature. This higher temperature burns the PM off thefilter as well. Yet another means is to use fuel borne catalysts tofacilitate regeneration. In another approach, called a “catalyzed dieselparticulate trap,” a catalyst is applied directly to the filter itself,which reduces the temperature necessary for the PM to burn off. Finally,an oxidation catalyst can be used in front of the filter to facilitateburn off of the PM. Johnson Matthey's Continuously Regenerating Trap(CRT) is such a system. Diesel particulate traps can reduce PM by asmuch as 85% in some applications. Traps utilizing a catalyst can alsoreduce other pollutants besides PM (e.g., HC, CO, and PM) with use of acatalyst (as mentioned earlier). Conversely, these traps can becomeclogged with PM, soot, and ash and catalyzed versions can be poisoned.They also add cost and weight to vehicles.

Diesel particulate traps can use a number of different types of filters,including: ceramic monolithic cell fiber (Corning, NGK), fiber-woundfilter (3M), knitted fiber (BUCK), woven fiber (HUG, 3M), sintered metalfiber (SHW, HJS) or filter paper, among others. Suppliers of thesedevices and their related technologies include, but are not limited to,Donaldson, Engelhard, Johnson Matthey, HJS, Eminos, Deutz, Corning, ETG,Paas, and Engine Control Systems.

Selective catalytic reduction (SCR) is another example of anaftertreatment system. In this technology, a chemical capable of actingas a reducing agent, such as urea, is added before the exhaust reachesthe catalyst chamber. Urea hydrolyzes to form ammonia. The ammonia thenreacts with the NOx of the exhaust gas to yield N₂ gas, therebydecreasing NOx emissions. The ammonia may be directly injected or beheld in the form of solid urea, urea solution or in crystalline form. Anoxidation catalyst is often used in parallel with SCR to reduce CO andHC. Unfortunately, while SCR is effective in reducing NOx and has lowcatalyst deterioration with good fuel economy, it requires an additionaltank on the vehicle and an infrastructure for refilling the tank. It isalso dependent on end user compliance; companies and drivers arerequired to refill the tank in order to maintain the emissions control.Suppliers of SCR or its components include, but are not limited to,Engelhard, Johnson Matthey, Miratech Corporation, McDermott, ICT, SudChemie, SK Catalysts, and PE Systems. While only used in the U.S. on alimited basis, SCR is expected to be widely used in Europe to reduceemissions, particularly in the heavy duty truck market.

NOx adsorbers are materials that store NOx under lean conditions andrelease and catalytically reduce it under fuel rich conditions(typically every few minutes). This technology can work in both gas anddiesel applications, though gas provides a better fuel rich, hightemperature environment. NOx adsorbers reduce the levels of HC, NOx, andCO, but have little to no effect on PM. They can function under a widerange of temperatures. Conversely, NOx adsorbing capacity decreasesbased on temperature, requires engine controls and sensors, and isfunctionally hindered or disabled by the sulfur content in fuel. Indiesel applications, there are additional constraints, including thequantity of oxygen present in the exhaust, the HC utilization rate, thetemperature range, and smoke or particulate formation.

A NOx reduction catalyst can also be used to control emissions by 1)actively injecting reductant into the system ahead of the catalystand/or 2) using a washcoat with a zeolite that adsorbs HC, thus creatingan oxidizing region conducive to reducing NOx. While this technology canreduce NOx and PM, it is more expensive than many other technologies andcan lead to poor fuel economy or sulfate particulates.

HC adsorbers are designed to trap VOCs while the catalyst is cold andthen release them once the catalyst is heated. This can be done by 1)coating the adsorber directly onto the catalytic converter substrate,which allows for minimal changes but less control, 2) locating theadsorber in a separate, but connected exhaust pipe before the catalyticconverter and having the air switch channels once the converter isheated, and/or 3) placing the adsorber after the catalyst. The last twooptions require a cleaning option for the adsorber. While thistechnology reduces cold start emissions, it is difficult to control andadds cost.

Since emissions have proven difficult to control, emissions controltechnologies are often combined in a system. Examples of combinationsystems include: a DeNOx and DPT (such as HJS′ SCRT system), a catalyticconverter placed in the muffler, SCR integrated with the muffler, or acatalyzed diesel particulate filter.

ACERT is another example of a system incorporating multiple emissionscontrol technologies. ACERT, from Caterpillar, targets four areas—intakeair handling, combustion, electronics, and exhaust aftertreament. Keycomponents include single and series turbocharging for cooling intakeair; variable valve actuation for improving fuel burns; electronicmultiplexing for integrating computer control; and catalytic conversionfor reducing tailpipe particulate emissions. Working in concert, thesesubsystems allow the company to increase fuel savings. A significantweakness of this technology is the high volume of catalyst needed.

There are many other emissions control technologies, some of which arenot yet technically feasible.

Catalytic Converters

The concerns of pollution caused partly by the automobile led to theClean Air Act of 1970 which required 90 percent reductions in autoexhaust. The mandatory reduction was considered controversial by somebut generally recognized as an advance for clean air and better health.

The automobile industry initially offered resistance to the new proposedregulations. Part of the resistance may have stemmed from theindustries' development of improved fuels. From the mid 1920's until themid 1980's, motor gasoline fuel contained an additive, tetraethyllead(TEL). TEL improved fuel performance by preventing pre-ignition in thecylinders of the engine. Pre-ignition results when the fuel/air mixtureignites prematurely in the combustion chamber of an engine. This resultsin damage to the engine and efficiency and power reducing caused byknocking.

To attain the reduced emission standards set by the government,engineers invented the catalytic converter. The catalytic converter wasadded to vehicle exhaust systems starting about 1976. The catalyticconverter was effective in reducing emissions to a certain degree.However, the common gasoline formulations containing TEL interfered withthe function of the catalytic converter. Because the TEL in the fuelpoisoned the metal catalysts of the catalytic converter, TEL waseventually removed from fuel.

While many people may be aware that many vehicles have a catalyticconverter, it is generally an unappreciated piece of technology. Thepurpose of the catalytic converter is to convert, or change, exhaustgases that are pollutants to less harmful compounds, such as nitrogen(N₂, which makes up about 78% of the atmosphere), water (H₂O), andcarbon dioxide (CO₂, a product of photosynthesis in plants).

The catalytic converter is used to facilitate the conversion of theunwanted pollutants to relatively harmless molecules such as N₂, H₂O,and CO₂. Basically, the catalytic converter provides a surface on whichthe pollutants are converted into the relatively harmless products. Acatalyst allows the reaction to proceed faster (or at a lowertemperature) by lowering the activation energy required. However, acatalyst is not used up in the reaction and can be used again (unlessthe catalyst is poisoned).

Typical pollutants in exhaust include nitrogen oxides (NOx), unburnedhydrocarbons, carbon monoxide, and particulate matter. The nitrogenoxides can be reduced to form nitrogen. When an NO or NO₂ moleculecontacts the catalyst, the catalyst facilitates removal of nitrogen fromthe molecule, freeing oxygen in the form of O₂. Nitrogen atoms adheringto the catalyst then react to form N₂ gas: 2NO=>N₂+O₂ and 2NO₂=>N₂+2O₂.

The carbon monoxide, unburned hydrocarbons, and particulate matter canbe further oxidized to form nonpollutants. For example, carbon monoxideis processed as shown: 2CO+O₂=>2CO₂.

The overall result of the catalytic converter is to complete thecombustion of fuel into nonpollutants.

Conventional catalytic converters have a number of limitations on theireffectiveness of eliminating pollutants. For example, if they arelocated too close to an engine, they can crack from overheating or aquick change in temperature. As such, the filters of the conventionalcatalytic converters cannot be placed immediately next to or inside anengine exhaust manifold, which is an optimal location to take advantageof the in situ high temperatures before the temperature decreases due toradiant cooling from the high thermal conducting properties of exhaustpipe material. Engine vibration and the quick change in temperaturesthat exist near and within the exhaust manifold would cause conventionalfilter material to fatigue and dramatically shorten the life of thefilters. In addition, some catalysts applied to conventional filterswork less efficiently or even cease to function at high temperatures,i.e., above 500 degrees Celsius. Accordingly, the conventional catalyticconverter filters are usually placed in the exhaust path in a locationaway from the engine.

Structures of Catalytic Converter and Particulate Filter

The components and materials of a catalytic converter are shownschematically in FIGS. 4 a and 4 b. The catalyst substrate is heldwithin the converter shell (also called a canister) using packaging mat(most often made of ceramic fibers). The converter is connected to thevehicle's exhaust system through the end cones, which can be eitherwelded to the shell or be formed as one part together with the shell,depending on converter packaging technology. The other components shownin the schematic—end seals and/or steel support rings—are optional; theyare usually not present in modern passenger car converters, but may berequired in more demanding applications, such as close-coupledconverters, large converters for heavy-duty engines, or dieselparticulate filters. Catalytic converters, especially those in gasolineapplications, can be also equipped with steel heat shields (not shown inthe schematic) to protect adjacent vehicle components from exposure toexcessive temperatures.

Generally, a catalytic converter is composed of at least five maincomponents: 1) a substrate; 2) a catalytic coating; 3) a wash-coat; 4) amatting; and 5) a canister. A general catalytic converter is shown inFigure X. In certain applications, as discussed in more detail below,the catalytic coating is optional.

Substrate

The substrate is a solid surface on which the pollutants can beconverted to the nonpollutants. Physically, a substrate provides theinterface for several molecular species, in any physical state such assolid, liquid, or gas, to react with each other. The substrate generallyhas a large surface area to provide a large area on which the pollutantscan be converted to nonpollutants.

Over the past decades, many different materials and designs have beentested to act as the substrate for chemical reactions. For example, mainphysical structures include honeycomb monoliths and beads. (See FIG. 1).The honeycomb structure contains numerous channels, usually runningparallel to each other along the length of the substrate. The substratehas channels that run the length of the substrate. The width of channelsvaries, often depending on the substrate material and applications forwhich it is used. These channels allow the exhaust gas to flow from theengine through the catalytic converter and out through exhaust pipe.While the exhaust gas flows through the channels of the substrate, thepollutant molecules are converted into nonpollutant molecules viachemical reactions and physical changes.

In the bead structure, the substrate is made of a collection of smallbeads (similar to putting a bunch of jelly beans in a tube). The exhaustcan flow around the beads (through the channels and crevices). Thepollutants are converted to nonpollutants as the exhaust gas hits thebeads. The bead structure was one of the early attempts to maximize thesurface area of substrate to which the exhaust molecules were exposed.

A number of different materials have been used as the substrate. Theseinclude ceramic, Fiber Reinforced Ceramic Matrix Composites (FRCMC),foam, powder ceramic, nanocomposite, metals, and fiber mat-typesubstrates. The most commonly used is a ceramic called cordierite, whichis produced by Corning. Cordierite is a ceramic formed from refractorypowders. FRCMC is an open celled foam wherein catalyst is disposed onthe walls of the cells, the foam being disposed within a catalyticchamber such that exhaust gas must pass through a cell path of the foamto exit. Foams are solids containing numerous pores that are formed bybubbles from gas and burned-off voids. Powder ceramic substrates aredifferent than cordierite and related ceramics in that the powderceramic is formed from sintered ceramic powders. Nanocomposites arematerials that use nano-powders and/or nano-fibers. Metals can also beused as a substrate. Generally, thin sheets of corrugated metal foil,such as steel, are rolled into a honeycomb-like structure. Fibermat-type substrates are materials that are woven on a small scale.Certain fiber mat-type substrates utilize NEXTEL fibers, produced by 3M.Additionally, “two-dimensional” non-woven fibrous composites have alsobeen tried where honeycomb structures were formed using rolled uppleating and/or corrugation. For example, see U.S. Pat. Nos. 4,894,070;5,196,120; and 6,444,006 B1.

Catalytic Coating

The third component of current catalytic converters is a catalyticcoating. As the name implies, the catalytic coating is the componentwhich actually catalyzes the conversion of pollutants to non-pollutants.

A catalyst is usually defined as a substance which influences the rateof a chemical reaction but is not one of the original reactants or finalproducts, i.e., it is not consumed or altered in the reaction. Inseveral known catalytic reaction mechanisms, the catalyst formsintermediate compounds with reactants but is recovered in the course ofthe reaction. Many other catalytic processes are not explained fully orunderstood in their entirety. Neither are the principles governing theselection and preparation of catalysts for specific purposes. Many ofthe developments in this field are achieved through elaborateexploration programs involving trials of countless materials. Catalystsare widely used in chemical and petrochemical processing to facilitatereactions which otherwise are too slow, or which require hightemperatures to yield good efficiencies. Catalysts are also used toconvert harmful components of engine exhaust gases, such as hydrocarbonsand carbon monoxide, into harmless substances, such as carbon dioxideand water vapor.

Catalysts are substances that have the ability to accelerate certainchemical reactions between exhaust gas components. In emission controlcatalysis, solid catalysts are used to catalyze gas phase reactions. Thecatalytic effect and the observed reaction rates are maximized byproviding good contact between the gas phase and the solid catalyst. Incatalytic reactors, this is usually realized by providing high catalyticsurface area through finely dispersing the catalyst on high specificsurface area carrier (support).

The catalytic coating is added to the substrate after the substrate isformed. The coating forms a layer on the surface of the substrate, thelayer containing the catalyst. Different types of catalysts are neededdepending, for example, on the chemical reaction, application needed,temperature conditions, economic factors, etc. A number of metalcatalysts are known in the art. For example, the most commonly used areplatinum, palladium and rhodium. Significant research has been done todevelop new catalysts.

The rate of chemical reactions, including catalytic reactions, generallyincreases with temperature. A strong dependency of conversion efficiencyon temperature is a characteristic feature of all emission controlcatalysts. The conversion, near-zero at low temperatures, increasesslowly at first and then more rapidly, to reach a plateau at high gastemperatures. When discussing combustion reactions, the term light-offtemperature is commonly used to characterize this behavior. The catalystlight-off is the minimum temperature necessary to initiate the catalyticreaction. Due to the gradual increase of the reaction rate, the abovedefinition is not very precise. By a more precise definition, thelight-off temperature is the temperature at which conversion reaches50%. That temperature is frequently denoted T₅₀. When comparingactivities of different catalysts, the most active catalyst will becharacterized by the lowest light-off temperature for a given reaction.

In some catalyst systems, increasing the temperature may increase theconversion efficiency only up to a certain point, as illustrated by thedashed line (B) in FIG. 4. Further temperature increase, despiteincreasing reaction rates, causes a decrease in the catalyst conversionefficiency. The declining efficiency is usually explained by othercompeting reactions which deplete the concentrations of reactants or bythermodynamic reaction equilibrium constrains.

The temperature range corresponding to the high conversion efficiency isfrequently called the catalyst temperature window. This type ofconversion curve is typical for selective catalytic processes. Goodexamples include selective reduction of NO by hydrocarbons or ammonia.

Another important variable influencing the conversion efficiency is thesize of the reactor. The gas flow rate through a catalytic reactor iscommonly expressed, relative to the size of the reactor, as spacevelocity (SV). The space velocity is defined as the volume of gas,measured at standard conditions (STP), per unit time per unit volume ofthe reactor, as follows: (3)SV=V/V_(r) where V is the volumetric gasflow rate at STP, m³/h; V_(r) is the reactor volume, m³, and SV has thedimension of reciprocal time which is commonly expressed in 1/h or h⁻¹.

In various catalytic emission control applications, the space velocitiesrange from 10,000 1/h to 300,000 1/h. Space velocities for monolithicreactors are calculated on the basis of their outside dimensions, e.g.,diameter and length of a cylindrical ceramic catalyst substrate. Sincethis method does not take into account the geometric surface area of thesubstrate, cell density, wall thickness, or catalyst loading, it is notalways appropriate for catalyst comparisons. Nevertheless, it is acommonly used and widely accepted industry standard.

Typical platinum loadings in filters used for off-road engines throughthe 1990's were between 35 and 50 g/ft³. These filters, installed onrelatively high polluting engines, required minimum temperatures ofnearly 400° C. for regeneration. Later, when catalyzed filters wereapplied to much cleaner urban bus and other highway vehicle engines, itwas found that they were able to regenerate at much lower temperatures.However, higher platinum loadings were needed to support the lowtemperature regeneration. Filters used in clean engine, low temperatureapplications have typically platinum loadings of 50-75 g/ft³.

Wash Coat

In most cases, the catalytic coating includes a wash coat as a fourthcomponent. The washcoat is applied to the surface of the substrate,thereby increasing surface area of the substrate. The washcoat alsoprovides a surface to which the catalyst adheres. The metal catalyst maybe impregnated on this porous, high surface area layer of inorganiccarrier, (i.e., washcoat—the term “catalyst support” may be used todenote the ceramic/metallic substrate, as well as the carrier/washcoatmaterial).

A number of substances can be used as a washcoat. Substances which arewidely used for catalyst carriers include activated aluminum oxide andsilicone oxide (silica).

The washcoat is a porous, high surface area layer bonded to the surfaceof the support. Its exact role, which is certainly very complex, is notclearly understood or explained. The main function of the washcoat is toprovide very high surface area, which is needed for the dispersion ofcatalytic metals. Additionally, the washcoat can physically separate andprevent undesired reactions between components of a complex catalyticsystem.

Washcoat materials include inorganic base metal oxides such as Al₂O₃(aluminum oxide or alumina), SiO₂, TiO₂, CeO₂, ZrO₂, V₂O₅, La₂O₃ andzeolites. Some of them are used as catalyst carriers. Others are addedto the washcoat as promoters or stabilizers. Still others exhibitcatalytic activity of their own. Good washcoat materials arecharacterized by high specific surface area and thermal stability. Thespecific surface area is determined by nitrogen adsorption measurementtechnique in conjunction with mathematical modeling known as the BET(Brunauer, Emmet, and Teller) method. Thermal stability is evaluated byexposing samples of given material to high temperatures in a controlledatmosphere, usually in the presence of oxygen and water vapor. The lossof BET surface area, which is remeasured at different time intervalsduring the test, indicates the degree of thermal deterioration of thetested material.

The washcoat can be applied to the catalyst support from a water basedslurry. The wet washcoated parts are then dried and calcined at hightemperatures. The quality of the catalyst washcoat can significantlyinfluence the performance and durability of the finished catalyst. Sincethe noble metal is subsequently applied to the washcoated parts byimpregnation, i.e., “soaking” the washcoat porosity with the catalystsolution, the washcoat loading will determine the noble metal catalystloading in the finished product. Therefore, it is extremely importantthat the washcoating process produces a very repeatable and uniformwashcoat layer. The details on the washcoating process and itsparameters are guarded as trade secrets by all catalyst makers.

Canister

The substrate is packaged into a canister, e.g., a steel shell, to forma catalytic converter. The canister performs a number of functions. Itholds the catalyzed substrate and protects the substrate from theexternal environment. Additionally, the canister forces exhaust gas toflow through and/or over the catalyzed substrate.

The catalyzed substrate can be also packaged inside mufflers, which arethen referred to as “catalyst mufflers” or “catalytic mufflers.” In thiscase, one steel canister holds both the catalyst and the noiseattenuation components, such as baffles and perforated tubing. Catalystmufflers can offer more space saving design compared to the combinationof a catalytic converter and a muffler.

The catalyzed substrate is usually placed inside the canister having aconfiguration made according to one of several methods, including:clamshell, tourniquet, shoebox, stuffing, and swaging, as shown in FIG.36.

Matting

In addition to the canister, a matting material is often used to packagethe catalytic substrate in the canister. The packaging mats, usuallymade of ceramic fibers can be used to protect the substrate and todistribute evenly the pressure from the shell. The mats often includevermiculite, which expands at high temperatures, thus compensating forthe thermal expansion of the shell and providing adequate holding forceunder all operating conditions.

For example, ceramic monoliths are wrapped in a special packagingmaterial which holds them securely in the steel housing, uniformlydistributing pressure and preventing cracking. Ceramic fiber mats aremost commonly used for packaging of catalytic converters for bothgasoline and diesel applications. These packaging mats can be classifiedas follows: intumescent (heat-expandable) mats; conventional (highvermiculite); reduced vermiculite; non-intumescent mats; or hybrid mats.

Heat Insulation

In many applications, the catalytic converter must be heat insulated toavoid damage to surrounding vehicle components (e.g., plastic parts,fluid hoses) or—in converters mounted closer the engine—to prevent anincrease of engine compartment temperature. One of the methods ofconverter thermal management is to employ a steel heat shield positionedaround the converter body. An alternative method is to provide aninsulation layer inside the shell by either (1) increasing the thicknessof the mounting mat, or (2) providing an additional layer of dedicated,low thermal conductivity insulation. While heat shields have beentraditionally used in the underfloor location, it has been suggestedthat increased mat thickness offers the best solution for convertersinstalled in the engine compartment (Saïd Zidat and Michael Parmentier,“Heat Insulation Methods for Manifold Mounted Converters,” DelphiAutomotive Systems, Technical Centre Luxembourg, SAE Technical PaperSeries 2000-01-0215). One of the advantages of using thicker mat ratherthan the heat shield is the lower average mat temperature, whichminimizes the risk of destroying vermiculite mats in close-coupledgasoline engine applications.

Particulate Trap

Another device for removing pollutants from an exhaust gas is aparticulate trap. A common particulate trap used on diesel engines is adiesel particulate trap (DPT). A main purpose of a particulate trap isto filter and trap particulate matter of various sizes from a stream offluid, such as an exhaust gas flow. The effectiveness of a particulatefilter is generally measured in its ability of filtering PM of differentsize, e.g., PM-2.5 and PM-10.

Diesel traps are relatively effective at removing carbon soot from theexhaust of diesel engines. The most widely used diesel trap is thewall-flow filter which filters the diesel exhaust by capturing the sooton the porous walls of the filter body. The wall-flow filter is designedto provide for nearly complete filtration of soot without significantlyhindering the exhaust flow.

As the layer of soot collects on the surfaces of the inlet channels ofthe filter, the lower permeability of the soot layer causes a pressuredrop across the filter and a gradual rise in the back pressure of thefilter against the engine, causing the engine to work harder, thusaffecting engine operating efficiency. Eventually, the pressure dropbecomes unacceptable and regeneration of the filter becomes necessary.In conventional systems, the regeneration process involves heating thefilter to initiate combustion of the carbon soot. In certaincircumstances, the regeneration is accomplished under controlledconditions of engine management whereby a slow burn is initiated andlasts a number of minutes, during which the temperature in the filterrises from about 400-600° C. to a maximum of about 800-1000° C.

In certain applications, the highest temperatures during regenerationtend to occur near the exit end of the filter due to the cumulativeeffects of the wave of soot combustion that progresses from the entranceface to the exit face of the filter as the exhaust flow carries thecombustion heat down the filter. Under certain circumstances, aso-called “uncontrolled regeneration” can occur when the onset ofcombustion coincides with, or is immediately followed by, high oxygencontent and low flow rates in the exhaust gas (such as engine idlingconditions). During an uncontrolled regeneration, the combustion of thesoot may produce temperature spikes within the filter which canthermally shock and crack, or even melt, the filter. The most commontemperature gradients observed are radial temperature gradients wherethe temperature of the center of the filter is hotter than the rest ofthe substrate and axial temperature gradients where the exit end of thefilter is hotter than the rest of the substrate.

In addition to capturing the carbon soot, the filter also traps metaloxide “ash” particles that are carried by the exhaust gas. Usually,these ash deposits are derived from unburnt lubrication oil thataccompanies the exhaust gas under certain conditions. These particlesare not combustible and, therefore, are not removed during regeneration.However, if temperatures during uncontrolled regenerations aresufficiently high, the ash may eventually sinter to the filter or evenreact with the filter resulting in partial melting.

It would be considered an advancement in the art to obtain a filterwhich offers improved resistance to melting and thermal shock damage sothat the filter not only survives the numerous controlled regenerationsover its lifetime, but also the much less frequent but more severeuncontrolled regenerations.

Continuous Regeneration Trap

One conventional method for catalytic conversion is a diesel particulatetrap (“DPT”). A DPT is a filter that collects particulate matter in theexhaust. The collected particulate matter must then be burned off beforethe filter becomes clogged. Burning off the particulate matter isreferred to as “regeneration.” Several conventional methods exist forregeneration of DPTs. First, an application of precious metal catalystsor base-metal catalyst to the surface of the filter can reduce thetemperature needed for oxidation of particulate matter. Second, thefilter can be preceded with a chamber containing oxidation catalyst thatcreates NO₂, which helps to burn off particulate matter. Third, thesystem can utilize fuel-born catalysts. Finally, external source of heatmay be employed, wherein soot burns at 550 degrees Celsius withoutcatalysts or approximately 260 degrees Celsius with precious metalcatalysts. Regeneration leaves behind ash residue as the carbon burns,requiring constant maintenance to clean the filter.

Yet another conventional method utilizes diesel oxidation catalysts(“DOCs”). DOCs are catalytic converters that oxidize CO andhydrocarbons. Hydrocarbon activity extends to the polynuclear aromatichydrocarbons (“PAHs”) and the soluble organic fraction (“SOF”) ofparticulate matter. Catalyst formulations have been developed thatselectively oxidize the SOF while minimizing oxidation of sulfur dioxideor nitric oxide. However, DOCs may produce sulfuric acid and increasethe emission of NO₂.

The function of the catalyst in the catalyzed diesel particulate filter(CDPF) is to lower the soot combustion temperature to facilitateregeneration of the filter by oxidation of diesel particulate matter(DPM) under exhaust temperatures experienced during regular operation ofthe engine/vehicle, typically in the 300-400° C. range. In the absenceof the catalyst, DPM can be oxidized at appreciable rates attemperatures in excess of 500° C., which are rarely seen in dieselengines during real-life operation. Reported substrates used in thesecatalyst applications include cordierite and silicon carbide wall-flowmonoliths, wire mesh, ceramic foams, ceramic fiber media, and more. Themost common type of a CDPF is the catalyzed ceramic wall-flow monolith.

Catalyzed ceramic traps were developed in early 1980's. Their firstapplications included diesel powered cars and, later, underground miningmachinery. Catalyzed filters were commercially introduced for Mercedescars sold in California in 1985. Mercedes models 300SD and 300D withturbocharged engines were equipped with 5.66″ diameter×6″ filters fittedbetween the engine and the turbocharger.

The use of diesel traps on cars was later abandoned, due to such issuesas insufficient durability, increased pressure drop, and filterclogging. Today, even though not all of these problems have been solved,catalyzed ceramic traps remain one of the most important diesel filtertechnologies. CDPFs are increasingly used in a number of heavy-dutyapplications, such as urban buses and municipal diesel trucks. For anumber of years, limited quantities of catalyzed filters have been alsoused in underground mining (North America and Australia) and in certainstationary engine applications.

Catalyzed ceramic filters are commercially available for a number ofhighway, off-road, and stationary engine applications as both OEM andaftermarket (retrofit) product. The list of suppliers includesEngelhard, OMG dmc2, as well as several smaller emission controlmanufacturers who specialize primarily in the off-road markets.

The main component of conventional filters is a ceramic (typicallycordierite or SiC) wall-flow monolith. The porous walls of the monolithare coated with an active catalyst. As the diesel exhaust aerosolpermeates through the walls, the soot particles are deposited within thewall pore network, as well as over the inlet channel surface. Thecatalyst facilitates DPM oxidation by the oxygen present in exhaust gas.

Pressure Drop

The flow of exhaust gas through a conventional catalytic convertercreates a substantial amount of backpressure. The backpressure buildupin a catalytic converter is an important attribute to catalyticconverter success. If the catalytic converter is partially or whollyclogged, it will create a restriction in the exhaust system. Thesubsequent buildup of backpressure will cause a drastic drop in engineperformance (e.g., horsepower and torque) and fuel economy, and may evencause the engine to stall after it starts if the blockage is severe.Conventional attempts to reduce pollutant emissions are very expensive,due to both the cost of materials and retrofitting or manufacturing anoriginal engine with the appropriate filter.

High filtration efficiencies of wall-flow filters are obtained at theexpense of relatively high pressure drop which increases with the filtersoot load. Initially, the filter is clean. As the particulate startdepositing within the pores in monolith walls (depth filtration), thepressure drop starts increasing with time in a non-linear manner. Thisphase is called the initial loading phase, during which pore attributeslike permeability and filter porosity continuously change due to theincreasing soot deposit inside the pore network. After the filtrationcapacity of the pores becomes saturated, soot starts depositing as alayer inside the inlet monolith channels (cake filtration phase). Alinear increase in pressure drop with time (and with soot load) isobserved during this period. One property that changes is the thicknessof the soot layer. Some authors also distinguish an intermediate shorttransition phase, from the moment the particulates start depositing onthe channel surface until the soot layer is fully established (Tan, J.C., et al., 1996, “A Study on the Regeneration Process in DieselParticulate Traps Using a Copper Fuel Additive”, SAE 960136; Versaevel,P., et al., 2000, “Some Empirical Observations on Diesel ParticulateFilter Modeling and Comparison Between Simulations and Experiments”, SAE2000-01-0477).

Pressure drop modeling in clean filter substrates has been done.Relatively simple models that have been developed show excellentagreement with experimental results (Masoudi, M., et al., 2000,“Predicting Pressure Drop of Wall-Flow Diesel Particulate Filters—Theoryand Experiment”, SAE 2000-01-0184; Masoudi, M., et al., 2001,“Validation of a Model and Development of a Simulator for Predicting thePressure Drop of Diesel Particulate Filters,” SAE 2001-01-0911). Most ofthe filter pressure drop in real applications, however, is created bythe soot deposit. In practical applications, the pressure drop of theclean wall-flow filter can be in the range of 1 to 2 kPa, while a loadedfilter pressure drop of 10 kPa can be considered in certaincircumstances low to moderate.

The total pressure drop of the particulate loaded filter, can be dividedinto the following four components: pressure drop due to suddencontraction and expansion at the inlet and outlet from the filter;pressure drop due to channel wall friction; pressure drop due topermeability of particulate layer; and pressure drop due to wallpermeability.

Pressure drop due to sudden contraction and expansion at the inlet andoutlet from the filter is similar to the same component in the cleanfilter, except that the effective channel size (hydraulic diameter) isnow smaller due to the soot layer, resulting in more gas contraction.

Pressure drop due to channel wall friction also increases relative tothe clean filter scenario, due to the decrease in the channel hydraulicdiameter. With thick soot layers, ΔPchannel can become a verysignificant contributor to the total pressure drop.

Pressure drop due to permeability of particulate layer (ΔPparticulate)is can be a significant contributor to the total pressure drop.

Pressure drop due to wall permeability (ΔPwall) is now also higher thanin the clean filter, because the wall pores are partly filled with soot.The increase in ΔPwall that can be attributed to the initial sootloading phase in the pores is represented by ΔPI in FIG. 23.

The total pressure drop can be expressed as follows:ΔP=ΔPin/out+ΔPchannel+ΔPparticulate+ΔPwall

Mathematical modeling of the pressure drop in soot loaded diesel filtersbecomes a complex and difficult task. Important properties of soot, suchas the permeability and packing density, depend on the application,engine operating conditions, and other parameters. There is an ongoingeffort to simulate pressure drop in wall-flow filters and increasinglymore sophisticated models are being developed. Predicting the actualsoot loading may require a theoretical model of the regeneration processitself.

Types of Catalytic Converters and Particulate Filters

Catalytic converters can be classified based on a number of factorsincluding: a) the type of engine on which the converter is used, b) itslocation relative to the engine, c) the number and type of catalystsused in the converter, and d) the type and structure of the substrateused. In addition each of these catalytic converters are often used inconjunction with other emission-control devices, such as CRT, EGR, SCR,ACERT, and other devices and methods.

Engine

Catalytic converters are used on at least two types of engines: gasolineand diesel. Within these two general classes, there are numerous typesof specific gasoline and diesel engines. For example, gasoline anddiesel engines are manufactured having varying displacements andhorsepower. Certain engines are equipped with a turbocharger and/or anintercooler. Most car and truck engines are water-cooled, while manymotorcycle engines are air-cooled. Certain utilities require highavailable horsepower, while others maximize fuel economy. All of thesevariables, in addition to others, may affect the level of pollutantsproduced during combustion of the fuel. Moreover, depending on the useof the engine, e.g., on-road, off-road, or stationary, there aredifferent regulatory requirements with respect to emissions standards.

Location

The catalytic converter can theoretically be placed anywhere along theexhaust stream of an engine. However, physical characteristics ofconventional catalytic converters limit their location. Most commonly invehicles, the catalytic converter is placed some distance from theengine block, closer to the muffler and underneath the body of the car.The catalytic converter is usually not placed close to the enginebecause the catalytic converter can fail for several reasons. Suchreasons include extreme temperatures, thermal shock, mechanicalvibration, mechanical stress, and space limitations near the engine.Also, physical setups of stationary engines may limit the location of acatalytic converter or particular filter.

For example, in its 2004 FOCUS™, Ford Motor Company managed to deploy amani-cat as did Honda Motor Corporation in one of its offerings. Thesesystems are in actuality adjacent to, rather than part of, the manifold.The higher temperatures and the extreme vibrational energy generated bycylinder explosions and moving parts would subject current catalyticconverters, if placed in a manifold, to extremes in thermal and physicalshock. Additionally, a design for a mani-cat was proposed by NorthupGrumman Corporation in U.S. Pat. No. 5,692,373. It is believed that eventhe current cordierite substrate would find such an environmentchallenging to endure.

In other applications, for example such as motorcycles (e.g.,Harley-Davidson), the presence of a catalytic converter in certainlocations can cause serious injury to the user. Because of the highoperating temperatures of a catalytic converter, it would be preferableto use a catalytic converter that is less prone to causing injury to auser, e.g., a smaller catalytic converter, a converter that does not getas hot, etc.

In certain instances, the exhaust system (for example, in a car) maycontain more than one catalytic converter or particular filter along itsexhaust flow. (See FIG. 4). For example, an exhaust system may have anadditional catalytic converter between the engine and the main catalyticconverter. This configuration is referred to as a pre-cat. The pre-catmay have denser configuration. Another set-up is a back-cat, which hassecond catalytic converter behind (or after) the main catalyticconverter. The back-cat is also sometimes used for a retrofit catalyticconverter.

Two Way vs. Three Way vs. Four Way

Catalytic converters can generally be classified as being a two-way,three-way, or four-way converter. There are at least the following typesof converters commercially available: oxidation converters, three-wayconverters (no air), three-way-plus oxidation converters, and four-wayconverters.

Oxidation (two-way) converters represent the early generation ofconverters that were designed to oxidize hydrocarbons (HC) and carbonmonoxide (CO). Although these units represent the most basic form ofcatalytic converter technology, they remain a viable pollution reductionoption in some areas. Oxidation converters usually contain platinum orpalladium. However, other non-noble metals can be used as well.

In the early 1980s, most vehicle manufacturers began using convertersdesigned to reduce NOx, in addition to oxidizing HC and CO. Thesethree-way converters, which were used in conjunction with computercontrolled engine systems and oxygen sensors, were employed to moreprecisely control the air to fuel ratio. These converters are referredto as three-way converters because they deal with three compounds: HC,CO and NOx.

Most modern cars are equipped with “three-way” catalytic converterstypically having one or more substrates in tandem using Corning's clayextrusion technology. “Three-way” refers to the three regulatedemissions the converter helps to reduce: carbon monoxide, volatileorganic compounds (VOCs, e.g., unburned hydrocarbons), and NOxmolecules. Such converters use two different types of catalysts, areduction catalyst and an oxidization catalyst.

In a three-way catalytic converter, the reduction catalyst is usuallyfound in the first stage of the catalytic converter and serves toreverse the oxidation of nitrogen that occurred in the combustionchamber. It commonly uses platinum and rhodium to help reduce NOxemissions. The oxidation catalyst, which can be composed of metals suchas platinum and/or palladium, is commonly located in a second region ofthe catalytic converter.

Three-way converters that have a reduction and an oxidation catalysttogether in one housing are sometimes called three-way-plus-oxidationconverters. These converters use air injection between the twosubstrates. This air injection aids the oxidation chemical reaction.

Four-way converters process carbon monoxide, nitrogen oxide, unburnthydrocarbons, and particulate matter. These include, for example, theQuadCAT Four-Way Catalytic Converter manufactured by Ceryx. It is acatalytic converter that that, according to its manufacturer, reducesfour of the major sources of air pollution—NOx, hydrocarbons, carbonmonoxide and particulate matter—to levels that will allow diesel enginesto meet 2002/2004 emissions standards. Others include those described inU.S. Pat. Nos. 4,329,162; and 5,253,476.

The catalytic converter, like other catalysts, facilitates reactions bylowering the activation energy required to accomplish the desiredreaction. For example, if particulates require a temperature of 550° C.before reacting with oxygen in the presence of catalysts, to burn off,this same reaction might require a temperature of only 260° C. Thislower energy threshold permits one physically to locate a catalyticsystem downstream from the engine where space is more abundant, eventhough temperatures are cooler. Otherwise, the catalytic system willneed to be placed upstream where temperatures are higher. However, thisis impractical with current technology because there is more potentialto damage the substrate when it is placed closer to the engine.

Diesel engines produce emissions that are high in NOx and particulatematter due to the high temperature and pressure, while relatively low COand hydrocarbon production. The compression combustion is less completethan with a spark of a gasoline engine. However, because of therelatively lean mixture with high air content, diesel is able to providebetter gas mileage than a gasoline engine. Three-way catalysts do notwork well in diesel exhaust due to the excess air. NOx reductioncatalysts typically require a well-maintained stoichiometric ratio offuel-to-air which cannot be easily done in diesel combustion engines.

Catalytic converter technology may be applied to various applications,including internal combustion engines and stationary combustion engines.The internal combustion engine is the most common engine used forvehicles. A catalytic converter is installed as a device in thevehicle's exhaust system, so the entire exhaust gas stream passesthrough the substrate, contacting the catalyst before being dischargedfrom the tailpipe. However, catalytic converters can be also part offairly complex systems involving various active strategies, such asinjection of reactants in front of the catalyst or sophisticated enginecontrol algorithms. Examples include a number of diesel catalyst systemsbeing developed for the reduction of NOx. The attributes of simplicityand passive character which have been listed among the advantages ofcatalysts may no longer apply to those systems.

Conventional attempts to reduce pollutant emissions can be veryexpensive, due partly to both the cost of materials and, in certainapplications, to retrofitting or manufacturing an original engine withthe appropriate filter.

Advances in Catalytic Converter and Particulate Filter Technology

An invention that lead to progress in catalytic converters was Corning'sdevelopment of extruded cordierite honeycomb monoliths. (See U.S. Pat.No. 4,033,779). Since the 1970's, more than a billion pounds ofpollutants have been removed from exhaust streams using this approachwhich employs catalysts (platinum, palladium, rhodium, etc.) from thenoble and base metal families firmly lodged in a washcoat on the surfaceof a rugged substrate (generally cordierite) that can withstand theextreme environment of an engine exhaust system. Variations andimprovements to this core technology have evolved in the years since,including variations in the placement of catalytic converters as well asin their composition and methods of manufacture. Still, however, thereremain fundamental inadequacies that, to date, have not been overcome.Currently, the state of technology is reaching physical and economicallimits with only minor improvements being made at great expense.

Limitations of Current Substrates

While the present state of catalytic converter and particulate matterfilter technology is useful to some degree for reducing emissionpollution, there are certainly drawbacks to the current technology.There are also characteristics that are not met by the present catalyticconverters. Some inadequacies are inherent to the type of substrateused. Accordingly, an improved substrate for use in a catalyticconverter or particulate filter would be a significant advance in thefundamental physical and chemical attributes of the materials used ascatalyst substrates in the catalytic converter. Moreover, an improvedsubstrate would dramatically enhance the quality and would enablemanufacturers and users to meet more easily the emissions standards of2007, and 2010, and later years.

The conventional monolithic catalytic converter substrate is generallyformed through an extrusion process. This process, which is bothcomplicated and relatively expensive, has been used for the pasttwenty-five years. However, there are limitations to the extrusionprocess. There is a limit as to how small channels can be created withinthe material and still maintain quality control. The extrusion processalso limits the shapes of the catalytic converters to cylinders orparallelograms, or shapes that have sides parallel to the extrusionaxis. This shape limitation has not been an issue with previous emissionstandards. However, the need to design a catalytic converter andparticulate filter able to reach near-zero emissions performance mayrequire non-linear and/or non-cylindrical filter design and vehicleintegration.

Decreasing the wall thickness increases the surface area, e.g., incertain instances, decreasing wall thickness from 0.006 inches to 0.002inches increases surface area by 54%. By increasing the surface area,more particulate matter may be deposited in less volume. FIG. 1 shows aprior art honeycomb configuration 102 formed within a ceramic filterelement 100 configured to increase the surface area for a catalyticconverter. The honeycomb configuration 102 is formed using an extrusionprocess in which long channels with their major axis parallel to theextrusion action are created. The opening of these channels faces theincoming exhaust airflow.

Progress in technology has allowed the manufacture of ceramic cordieritesubstrates with decreased wall thickness. The once standardconfiguration for passenger car applications, 400/6.5, of 400 cpsi celldensity and of 0.0065″ (or about 0.17 mm) was gradually replaced withsubstrates of thinner walls (0.0055 to 0.004 mil). However, the physicallimitations of this material have been approached. Because of thephysical characteristics of ceramics, in particular cordierite, usingsubstrates made of cordierite ceramics with even thinner walls is notpractical. The thinner-walled material is not able to meet othernecessary characteristics (e.g., durability, heat resistance).

Diesel catalysts, in part because of their larger sizes, often havethicker walls than their automotive counterparts. Because diesel wallflow filters generally have thicker walls, there are physicallimitations on the channels per square inch these filters can have.Generally, there are no commercially available diesel wall flow filtershaving more than 200 channels per square inch.

Another limitation of currently available substrates is their decreasedcatalytic efficiency at lower temperatures. When a converter system iscold, such as at engine start up, temperatures are not sufficiently highto commence the catalytic reactions. The cordierite, silicon carbide,and various metal substrates employed in catalytic converters andmarketed by Corning, NGK, Denso, and other companies today are fashionedfrom very tough, dense materials with excellent mechanical strength andtolerances for thermal shock and vibration. However, these materialsrequire time to absorb heat after start up to reach temperaturessufficient for catalytic reactions. Due to the delay in the catalysisreaction start-up, it is estimated that approximately 50% of all of theemissions from modern engines are released to the atmosphere during thefirst 25 seconds of engine operation. Even a small improvement duringthese critical “cold start” seconds could drastically improve the amountof pollutants successfully treated annually. While effort has beeninvested to address this problem, there remains a need for a catalyticconverter that can reduce emissions during this critical cold startperiod. Even the most advanced and expensive state of the art,cordierite-based catalytic converter requires approximately 20 secondsto start up.

To more quickly achieve reaction temperatures, attempts have been madeto move the converters closer to the engine exhaust manifold wherehigher temperatures are more quickly available and also serve to drivereactions more vigorously during operation. Because usable space underthe hood of a vehicle is limited, the size of converter systems, andtherefore the amount of throughput that can be successfully treated, islimited. Current substrates cannot be effectively used in the enginecompartment of vehicles. Moreover, adding additional weight to theengine compartment is undesirable, and many current substrates are denseand have limited porosity (roughly 50% or less), requiring systems thatare both weighty and voluminous to treat large scale exhaust output.Additionally, substrates such as cordierite are susceptible to meltingunder many operating conditions, thereby causing clogs and increasedback pressure.

Other methods of compensating for cold starts include elaborateadsorption systems to store NOx and/or hydrocarbons temporarily so thatthey might be treated once the converter has reached criticaltemperatures. Some of these systems require parallel piping andelaborate adsorption surfaces, additional valves and control mechanisms,or multiple layers of differing washcoats used to adhere catalysts tosubstrates and to segregate reaction environments. This problem isespecially challenging in diesel engines where large volumes of sootparticulates, NOx, and SOx may need to be trapped. In some large,industrial diesel engines, rotating banks of diesel particulate trapsare used to collect, store, and subsequently treat particles. (In stillother systems, NOx is stored and used as an oxidizing agent to convertCO into CO₂ while it is reduced to N₂.)

Given regulatory restrictions on total emissions, a system that couldreadily curtail even some of the 50% of emissions that occur during coldstart might obviate the need for some of the expensive and elaboratework-arounds described above. Used in conjunction with these workarounds, such a system could result it in substantially decreasedemissions. However, as explained above, conventional systems aregenerally complicated and expensive and also tend to misfire and/or workunpredictably.

Another inherent limitation of conventional systems is the typical“residence time” required to burn off particulates. When one considersthe large volume of exhaust gas throughput during operation and thespeed at which the gas must flow, it is important that a converter becapable of rapid light off. Thus, a catalytic converter capable of rapidlight off, of enduring extreme thermal and vibrational shocks, andcapable of rapid internal temperature build up during cold starts, wouldgreatly enhance the capability of industry to reduce emissions, meetupcoming environmental standards for 2007 and 2010, and produce cleaneroperating cars, trucks, buses, and heavy industrial engines.

If the substrate were also lightweight, it would also result in improvedmileage statistics on new vehicles. To date, however, no substrate hasbeen identified capable of addressing many or all of these problems.

Design Considerations for a Substrate for a Catalytic Converter orParticulate Filter

Catalyst substrate is a crucial component influencing performance,robustness, and durability of catalytic converter systems. Furthermore,filtering substrates significantly affect the operating performance ofparticulate filters. Ideally, the substrate used in a catalyticconverter or particulate filter should have a number of attributes.These attributes include, but are not necessarily limited to, one ormore of the following aspects: a) surface area; b)porosity/permeability; c) emissivity; d) heat conductance; f) thermalattributes such as shock resistance, expansion, and conductance; g)density; h) structural integrity; i) efficiency of pollutant treatment;j) amount of catalyst required; and k) weight of the system. A catalyticor filtering substrate that optimizes one or more attributes would be anadvance in the field of filtering fluids and catalyzing reactions.

BRIEF SUMMARY OF THE INVENTION

Various embodiments are described in this summary. These, as well asother embodiments of the invention, are described in the followingDetailed Description section.

The inventor has discovered that a non-woven Sintered Refractory FibrousCeramic (nSiRF-C) composite, as described herein, can be used as andshaped into an improved substrate for catalytic converters, particulatefilters, and related devices.

The inventor has also discovered that an improved catalytic substrateand improved filtering substrate can be prepared from a material havingparticular attributes as described herein. For example, suitableattributes include high melting point, low heat conductance, lowcoefficient of thermal expansion, ability to withstand thermal andvibrational shock, low density, and very high porosity and permeability.An exemplary material in one embodiment that has these attributes is anSiRF-C.

One example of a material having suitable attributes is a nSiRF-Ccomposite. An example of a nSiRF-C is an alumina enhanced thermalbarrier (“AETB”) material or a like material, which can be used inaccordance with embodiments of the present invention as a catalyticsubstrate or a filtering substrate. AETB materials are known in the artand comprise aluminaboriasilica (also known as alumina-boria-silica,aluminoborosilicate, and aluminoboriasilicate) fibers, silica fibers,and alumina fibers. One commonly known application for AETB is as anexterior tile on the Space Shuttle, ideal for shuttle re-entry. AETB hasnot been used as a filtering substrate or a catalytic convertersubstrate.

It has been realized by the present inventor that the attributes thatmake AETB desirable to the space industry are also preferred incombustion technology. Among other attributes, AETB has a high meltingpoint, low heat conductance, low coefficient of thermal expansion,ability to withstand thermal and vibrational shock, low density, andvery high porosity and permeability. This combination of desiredattributes is lacking in current filtering and catalytic convertersubstrates.

It has also been discovered that nSiRF-C composites, such as AETB andsimilar suitable substrates, can be prepared, shaped, molded, cut,and/or fashioned (or otherwise modified physically) into new formssuitable for use as particulate filter and catalytic convertersubstrates.

The present invention has a number of advantages over currenttechnology. First, the present invention will lead to improved airquality and respiratory health. The present invention may substantiallyreduce the potential for carbon monoxide poisoning.

Embodiments of the present invention can be used as a direct substitutefor currently used catalytic and filtering substrates, as well ascatalytic converters and particulate filters, and exhaust and enginesystems. As described in fine detail below, the substrates of thepresent invention provides a number of advantages over prior artsubstrates and further solves a number of problems left unsolved by theprior art substrates. This can translate into significant cost savingson the part of the manufacturers. Because it is possible to use thepresent invention as a direct substitute for current technology, thereis no need to redesign exhaust systems. Thus, enhanced exhaust filteringand cleaning can be obtained without the need to retool manufacturingplants and lines and with only minimal investment in time.

The improved catalytic and filtering characteristics of the presentinvention require, in certain embodiments, the use of less catalyst.Because most catalysts used for the relevant applications are expensive,this advantage leads to another cost-saving.

The preferred thermal attributes of some embodiments of the presentinvention reduce and/or eliminate the need for certain parts of theexhaust system that deal with the heat build-up associated with currentcatalytic converters and particulate filters. Heat shields andinsulation may not be needed in certain embodiments of the presentinvention. Elimination of these components from exhaust systems andvehicles reduces cost only directly (components are not used, thus lowercosts of production) but also indirectly (the weight of a vehicle isreduced, thus reducing fuel costs). Other benefits may include betterperformance, better mileage, and/or better horsepower.

In certain embodiments, a conventional catalytic converter orparticulate filter can be replaced with the present invention that issmaller but has the same or better efficiency of removing pollutants.With a smaller catalytic converter or particulate filter, more space isavailable on the vehicle for other purposes. Furthermore, because thefilter or converter of the present invention is smaller, the overallweight of the vehicle is reduced.

Another aspect of some embodiments of the present invention is acatalytic substrate suitable for use in a catalytic converter that isplaced, either wholly or in part, in the head of an engine Saidcatalytic converter, referred to herein as head cat, has numerousadvantages over the prior art. For example, conventionally such a headcat is not practical because of the limitations of currently availablecatalytic substrates. The common substrate cordierite would absorb toomuch heat. Because of the preferred thermal characteristics of thesubstrate of the present invention, a head cat comprising said substratewould reduce turbo thermal stress on a turbocharger and/or intercoolerif present.

Also a head cat does not require additional external hardware such asheat shields. The use of a head cat permits the maintenance of preferredappearances of engines and products, such as in motorcycles. In certainembodiments, the use of a head cat also reduces external discolorationof the exhaust system, such as mufflers and header pipes. A number ofadditional advantages of the head cat in certain embodiments include oneor more of the following: increased safety; filters particles thatintercooler would otherwise pick up, hence improving life ofinter-cooler and providing a cost saving; no matting required in certainembodiments; rattling sounds in heat shields can be reduced oreliminated with the use of a head-cat; and the head cat can reduce thesize of the requisite muffler.

In other embodiments of the head cat; smaller particulate matter is moreefficiently burnt off. In case of failure of a head-cat, only one smallcat may need replacement. Head-cats are also provide these advantages tofor boats, watercraft, motorcycles, leaf-blowers etc.

More, different embodiments of the present invention provide one or moreof the following advantages over the prior art: improved appearance;avoidance of additional hardware; additional hardware (that might berequired due to tighter regulations) would not be necessary with thepresent invention; decreased or eliminated discoloration of muffler andexhaust pipes due to exothermic chemical reactions. The presentinvention allows in certain embodiments a smaller substrate, and thus asmaller muffler or canister in certain systems. The substrate of thepresent invention provides increased safety for systems using acatalytic converter or particulate filter because the substrate of thepresent invention has improved thermal properties and does not absorb asmuch heat as certain conventional substrates. Moreover, the substrate ofthe present invention cools off faster than many conventionalsubstrates, leading to increased safety. Certain embodiments of thepresent invention provide for improved resistance to temperature changeand therefore will not crack, fracture, or become damaged as much ascertain conventional substrates if there is a sudden temperature change.In certain embodiments, the substrate is easier to manufacture thanconventional substrates (e.g., a nSiRF-C wall flow substrate can bemanufactured from a single piece of material rather than pluggingchannels). This attribute saves not only time but also money.

In other embodiments, a nSiRF-C weighs less than conventionalaftertreatment devices. This attribute is not only important for cars,but also crucial in markets where weight is a factor (e.g., smallengines, motorcycles, personal watercraft, and performance cars).

In some embodiments, the substrate of the present invention exhibits aless backpressure than competing aftertreatment devices. This lowerbackpressure can results in increased vehicle performance, increasedhorsepower, and increases fuel economy.

Other embodiments of the invention are directed to, for example, amethod catalyzing reaction, a method of filtering a fluid, a process ofpreparing a catalytic substrate, a process of preparing a filteringsubstrate, a substrate prepared according to said processes, and othersas described in more detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a conventional cordierite substrateincorporating a honeycomb structure. The honeycomb configuration 302 isformed within the cordierite filter element 300. The honeycomb structure302 is formed using an extrusion process in which long channels (ortubes) with their major axis parallel to the extrusion action arecreated. The openings of these channels face the incoming exhaustairflow. As the emissions enter the channels, the particulate willdeposit along the interior septum of the tubes.

FIGS. 2 a and 2 b show micrographs of cordierite. In FIG. 2 b, sphere210 represents a PM-10 sized particle and sphere 225 represents a PM-2.5sized particle.

FIG. 3 is a micrograph of SiC 300.

FIG. 4 a is a longitudinal cross-sectional view of a typical catalyticconverter schematic diagram. The catalytic converter 400 includes areduction catalyst 402 and an oxidation catalyst 404. As exhaust flow406 enters the catalytic converter 400 it is filtered and exposed to thereduction catalyst 102 and then to the oxidation catalyst 404. Theexhaust flow 406 is then treated by the oxidation catalyst 404 whichcauses unburned hydrocarbons and carbon monoxide to burn further.

FIG. 4 b shows a schematic diagram of a catalytic converter.

FIG. 5 is a cross-sectional view of a schematic of three substrates ofhaving three different frontal surface shapes.

FIG. 6 is an example schematic diagram of a flow-through configurationof a catalytic or filtering substrate. The substrate has a plurality ofchannels 610 formed by channel walls 620. The fluid flow 630 enters thefrontal surface and travels through the channels 610 and exits the rearsurface.

FIG. 7 is an example schematic diagram of a wall-through configurationof a catalytic or filtering substrate. A wall-flow pattern is composedof the same substrate material 720 and channels 710, except the channels710 do not connect completely to the other side. Instead, the channels710 are formed as blind holes, leaving an undrilled portion 740 ofsubstrate 720 at the end of the channel 710. The fluid flow 730 thanpasses through a channel wall 720 before exiting the substrate at therear surface. One particular advantage of the present invention is thatfluid flow 730 in the wall-flow pattern has substantially the samecharacteristics as the flow-through pattern.

FIG. 8 is an example schematic diagram of a wall-through configurationof a catalytic or filtering substrate. In this instance, fluid flow 830enters the substrate at the frontal surface. Some of the fluid exits thesubstrate at the rear surface by flowing through an undrilled portion845.

Some channels

FIG. 9 is an end view of an embodiment of a substrate 900 that employswall flow channels. Alternating channels have an undrilled portion 920at either the ingress or egress. Drilled channels 910 alternate withundrilled portions 920 of channels drilled from the opposing side. As aresult, the substrate appears to have a “checkerboard” pattern ofchannels.

FIGS. 10 a-10 d show a comparison of frontal surface area 1020, 1021,1022, 1023 and number of cells 1010, 1011, 1012, 1012 is shown. In acomparison of FIGS. 10 a and 10 c, each embodiment has the same celldensity, i.e., number of channels or cells. However, FIG. 10 c has amuch higher frontal surface area. Ideally, the frontal surface area isminimized such that structural integrity still remains. A similarcomparison may be made between the embodiments of FIGS. 10 b and 10 d.Regarding FIGS. 10 a-10 d, the embodiment of FIG. 10 b has thepreferable structure; cell density is maximized and frontal surface areais minimized.

FIG. 11 shows an embodiment of square channels to scale. In thisembodiment, the cell void 1110 to cell wall 1120 ratio is 31.83:1.5, orapproximately 20:1.

FIG. 12 shows an embodiment of a substrate 1210 having an exemplifiedcell void to cell wall ratio shown to scale. The substrate 1210 is foursquare inches in length and width and comprises four squares 1220, 1221,1222, 1223 of 1⅛ inches by 1⅛ inches. Each of the four squares 1220,1221, 1222, 1223 is drilled to have a cell density of 900, for a totalsubstrate cell density of 3600. The wall thickness between the cells is1.5 mil. The spacing between each square 1220, 1221, 1222, 1223 on thesubstrate 1210 is ⅞ inches and the squares 1220, 1221, 1222, 1223 areeach approximately 7/16 inches from the closest edge of substrate 1210.

FIGS. 13 a-c is show several embodiments of the channels structure FIGS.13 a-13 c show hexagonal channels 1310, triangular 1320, and squarechannels 1330, respectively. These embodiments are all successful incarrying out the present invention because the walls 1315, 1325, 1335 ofthe channels 1310, 1320, 1320 are substantially parallel to each other.

FIGS. 14 a-d show an embodiment of the present invention. Themicroscopic view shows the substantially similar dimensions ofrectangular-shaped channels 1410, 1411, 1412, 1413 in a substrate 1415,1416, 1417, 1418. FIGS. 14 c and 14 d illustrate the fibers 1420, 1421present in the material. These fibers show the porosity, which issuperior to the platelets of cordierite in conventional systems.

FIG. 15 is a two-dimensional diagram of a comb 1500 that can be used ina combing method of preparing a catalytic or filtering substrate of thepresent invention.

FIG. 16 shows various views of a comb 1600 (or portion thereof) that canbe used in certain embodiments of the present invention. FIG. 16 alsoprovides exemplary physical dimensions in inches of comb 1600.

FIG. 17 is a schematic diagram of the surface area enhancements andentry and exit tubes which can be formed in the filter element ofembodiments of the present invention. FIG. 17 provides fluid flow 1704entering channel openings 1702 on the frontal surface. Fluid exits therear surface of the substrate at 1704 on the right hand side. Thesubstrate shown in FIG. 17 exemplifies a substrate having a wall-flowconfiguration, wherein the channels gradually decrease in size as thechannel extends from the channel opening through the substrate to thechannel terminus.

FIG. 18 is a longitudinal view (photograph) of an embodiment substrateembodiment of the present invention. A filter substrate 1800 of thepresent invention is shown. The substrate 1800 has a hard coating 1804on the outside wall 1802. For the sample shown in FIG. 18, the hardcoating consists of finely crushed cordierite and inorganic fibers. Apowder was also painted on the filter foundation 1800 and cured asdescribed herein. The hard coating protects and insulates the filterfoundation while not changing the dimensions.

FIG. 19 is a graphical display of the residence time required to burnparticulate matter at varying temperatures. It provides the residencetime required to combust or burn particulate matter (soot mass) atvarious temperatures. As seen, the residence time to combust or burnsoot mass having an initial 0.9 soot mass at 600 Kelvin is much longerthan the residence time at 1200 Kelvin.

FIG. 20 provides an exhaust substrate system 2000 including a substrate2002 combined with a wire mesh heating element 2004. The substrate 2002and wire mesh heating element 2004 are inserted into the exhaust casing2006 at an angle compared to the exhaust flow. Since the wire meshheating element 2004 is placed behind and below the substrate 2002 as aresult of the angle, the substrate 2002 can be heated more efficientlyand uniformly taking advantage of the known principal that heat rises.As previously discussed, more uniform and efficient heating enables thesubstrate 2002 to more completely combust or flash off the particulatesresulting in cleaner exhaust.

FIG. 21 is a diagram of a frontal view of the filter element 2102 andwire mesh heating element 2104 described and discussed in relation toFIG. 9. As can be seen the filter element 2102 and wire mesh heatingelement 2104 are oval shaped so as to fit in the casing at an angle. Theshape of the casing, shape of the filter element 2102, type of heatingelement 2104 and angle can all be modified to fit the requirements andrestrictions of the intended exhaust system application.

FIG. 22 a is a photomicrograph of a substrate of the present invention,specifically AETB.

FIG. 22 b is a photomicrograph of a substrate of the present invention,specifically AETB. Fiber 2205 can be seen. Sphere 2210 illustrates aPM-10 sized particle, and Sphere 2225 illustrates a PM-2.5 sizedparticle.

FIG. 23 is a graph showing pressure drop (delta P) as a function of gashourly space velocity (hr⁻¹) for seven materials: Corning 200/12 DPT at932 F (2340); AETB-11 having 600 cpsi, 6 mil wall thickness and 11lb/ft³ at 1100 F (2310); AETB-11 having 600 cpsi, 6 mil wall thicknessand 11 lb/ft³ at 932 F (2320); AETB-11 having 600 cpsi, 6 mil wallthickness and 11 lb/ft³ at 662 F (2330); cordierite having 400 cpsi and6 mil wall thickness at 1100 F (2350); cordierite having 400 cpsi and 6mil wall thickness at 932 F (2360); and cordierite having 400 cpsi and 6mil wall thickness at 662 F (2370). Data for cordierite are calculated.

FIG. 24 is a graph showing the % destruction versus temperature. Asubstrate of the present invention 2410 shows a greater percentage ofdestruction of material at lower temperatures than a cordieritesubstrate 2420.

FIG. 25 is a diagram of a cross sectional view of an embodiment of animproved catalytic converter of the present invention. In thisembodiment, the catalytic converter comprises a durable and heatresistant casing 2502. The casing 2502 has an intake 2504 and an exhaustport 2506. The improved substrate 2510 has one or a plurality of zones2512, 2514. The improved substrate 2510 is wrapped or enclosed in one ormore layers of matting/insulation 2515. The matting layer 2515 may beapplied to the filter foundation 2510 to shield the foundation 2510 fromengine and mobile environment vibrational shock as well as to insulatethe exterior environment from internal thermal temperatures of thefilter foundation 2510.

FIG. 26 is a shows a schematic of a catalytic converter or particularfilter 2600 having four substrates 2601 a, 2601 b, 2601 c, and 2601 darranged in a parallel fashion. The filter or converter has a frontalopening 2604 and an rear exit 2605.

FIGS. 27 a-d shows a catalytic converter or particulate filter 2700having stacked membrane configuration substrates 2710. The inlet port2720 and outlet port 2730 are fashioned at different heights. FIGS. 27 band 27 c show alternative embodiments.

FIG. 28 is a photograph of a substrate/filter in a wall flowconfiguration made according to an embodiment of the present invention,with the following attributes: 1 inch diameter by 1 inch thickness, thechannel pattern covered by 0.8 inch by 0.8 inch.

FIG. 29 is a graph that illustrates the drop in pressure measured in areactor-tube flow-measurement system as a function of gas flow rate fortemperature so 27° C., 29° C. and 400° C. for an embodiment of thepresent invention.

FIG. 30 is a graph that illustrates the drop in pressure measured in areactor-tube flow measurement system as a function of temperature at aconstant flow rate of 125 SLPM for an embodiment of the presentinvention.

FIG. 31 is a graph that illustrates the observed pressure drop forvarious substrates material density and wall-flow configuration as afunction of space hourly velocity. This particular test was conducted at932° F. temperature.

FIG. 32 is a graph that illustrates the observed pressure drop forvarious substrates material density and wall-flow configuration as afunction of space hourly velocity. This particular test was conducted at1100 Fahrenheit temperature.

FIG. 33 is a graph that illustrates the change in pressure as a functionof N₂ gas flowrate for the AETB-12 substrate/filter at 27° C. and 400°C.

FIG. 34 is a graph that illustrates the change in pressure as a functionof operating temperature for various N₂ gas flow-rates for AETB-12substrate/filter.

FIG. 35 is a graph that illustrates the change in pressure as a functionof N₂ gas flowrate for the AETB-12 substrate/filter at 29° C. and 400°C.

FIG. 36 illustrates various methods for placing a substrate in acanister.

FIG. 37 is a graph illustrating the emission limits for on-road heavyduty diesel vehicles.

FIG. 38 is a graph that illustrates improvements over various years inNOx and Particulates emissions from diesel engine exhaust.

FIG. 39 is a graph that illustrates particulate size distribution indiesel emissions.

FIG. 40 is a graph that illustrates the difference between depthfiltration and sieving (cake filtration).

FIG. 41 is a chart that contains various examples of wash coatings.

FIG. 42 is a schematic that illustrates a NOx adsorber system.

FIG. 43 is a schematic that illustrates an embodiment of the presentinvention positioned between an engine head and an exhaust manifold.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Overview

The present invention in certain embodiments is directed to a catalyticsubstrate suitable for use in a number of applications, including as asubstrate in a catalytic converter. Another aspect of the presentinvention is a filtering substrate suitable for use in a number ofapplications, including as a substrate in a particulate filter, such asa diesel particulate filter (DPF), or diesel particulate trap (DPT). Theinvention also provides an improved substrate for removing and/oreliminating pollutants from the exhaust of combustion engines. Thecatalytic substrate and filtering substrate provide, in certainembodiments, improvements in removing pollutants from an exhaust gas.The improvements include, but not limited to, one or more of thefollowing: faster light-off period, increased depth filtration of PM,less back pressure, lower probability of clogging, increased ability tobe placed in multiple locations in the exhaust system including themanifold or the head itself, high probability of catalytic reaction,high conversion ratios of NOx, HC, and CO, a faster burnoff of PM,minimization of catalyst material use, reduced weight of theafter-treatment exhaust system, and the like.

Other embodiments of the invention include catalytic converters,particulate filters, diesel particulate filters, diesel particulatetraps, and the like. The present invention also provides a process ofmaking or preparing the catalytic and filtering substrates, catalyticconverters, particulate filters, catalytic mufflers, and exhaustsystems. Other embodiments of the present invention include a pre-cat, aback-cat, a head-cat, and a mani-cat, each of which comprises asubstrate of the present invention. Additionally, the present invention,in alternative embodiments, is directed to a substrate made according tothe process described herein.

In another aspect, the present invention includes a catalytic substrateor filtering substrate that offers one or more of the followingattributes: a faster light-off period, increased depth filtration of PM,a lower backpressure, a lower probability of clogging up, an ability tobe placed in multiple locations in the exhaust system including themanifold or the head itself, a higher probability of catalytic reaction,a higher conversion ratios of pollutants such as NOx, HC, CO, fasterburnoff of PM, a lower amount of catalyst material needed, fasterlight-off in for cold starts, lower external wall temperature of thesubstrate, and the like.

Using a substrate, catalytic converter, particulate filter, or exhaustsystem of the present invention provides a number of advantages andimprovements over the prior art. In certain embodiments, these improvedcatalytic converters and/or particulate filters are able to removeand/or eliminate pollutants from the exhaust of combustion engines witha number of specific advantages, as described in more detail below.Improved exhaust systems are likewise an additional aspect of theinvention described herein. The improved exhaust system reduces theamount of pollutants emitted from the operated engine.

The present invention, including nonlimiting embodiments and examples,are described in more detail below. The embodiments discussed herein areprovided for illustrative purposes only. The invention is not limited tothese embodiments.

Catalytic Substrate

The present invention is directed to a catalytic substrate comprising,or alternatively consisting of or consisting essentially of, a non-wovenSintered Refractory Fibrous Ceramic (nSiRF-C) composite, as describedherein, that can be used in catalytic converters, particulate filters,and related devices; and optionally further comprising an effectiveamount of a catalyst, such as a catalytic metal. Preferably, thecatalytic substrate comprises a catalyst. The nSiRF-C composite can beshaped into configurations suitable for uses described herein.

The nSiRF-C composite is non-woven. In certain embodiments, the nSiRF-Ccomposite is a material having a definitive, rigid three-dimensionalshape. The fibers of the nSiRF-C composite are not arranged in anorganized pattern but are arranged three-dimensionally in a random,haphazard, or omnidirectional fashion. In some embodiments, the nSiRF-Cis in the form of a matrix.

The nSiRF-C is a sintered composite. In one embodiment, a sinteredcomposite is a cohesive mass formed by heating without melting. However,the process of sintering a ceramic material is well-known in the art,and thus the scope of the present invention is not necessarily limitedto specific embodiments and descriptions described herein. Sinteringcreates bonds without resin residue. With reference to the presentinvention, the sintered ceramic is a cohesive mass of dispersed fibersformed by heating without melting.

The nSiRF-C is a refractory fibrous ceramic composite. The nSiRF-C ofcertain embodiments is composed of high grade refractory fibers ofvarious lengths and compositions as exemplified in nonlimitingembodiments herein.

In one embodiment, the present invention is directed to a catalyticsubstrate suitable for use in a number of applications as describedherein. Such a substrate includes a number of materials which have oneor more, preferably a plurality of attributes as described herein. Thesubstrate of the present invention is made of a non-woven, fibrousceramic composite made from refractory grade fibers. Such a material isdisclosed in U.S. Pat. No. 4,148,962, which is incorporated herein byreference in its entirety. Other suitable materials are disclosed inU.S. Pat. No. 3,952,083.

In one embodiment, the catalytic substrate of the present inventioncomprises, or alternatively consists or consists essentially of, analumina enhanced thermal barrier (“AETB”) material or a like materialknown to one of ordinary skill in the art. AETB material is known in theart and more fully described in Leiser et al., “Options for ImprovingRigidized Ceramic Heatshields”, Ceramic Engineering and ScienceProceedings, 6, No. 7-8, pp. 757-768 (1985) and Leiser et al., “Effectof Fiber Size and Composition on Mechanical and Thermal Properties ofLow Density Ceramic Composite Insulation Materials”, NASA CP 2357, pp.231-244 (1984), both of which are hereby incorporated by reference.

In another embodiment, the catalytic substrate comprises Ceramic tiles,such as alumina enhanced thermal barrier (AETB) with toughened unipiecefibrous insulation (TUFI) and/or reaction cured glass (RCG) coatings.Such materials are known in the art.

Another suitable material is Fibrous Refractory Ceramic Insulation(FRCI). In one embodiment, AETB is made from aluminaboriasilica (alsoknown as alumina-boria-silica, aluminoborosilicate, andaluminoboriasilicate) fibers, silica fibers, and alumina fibers. Onecommonly known application for AETB is as an exterior tile on the SpaceShuttle, ideal for shuttle re-entry. AETB has a high melting point, lowheat conductance, and coefficient of thermal expansion, ability towithstand thermal and vibrational shock, low density, and very highporosity and permeability. Thus, in a preferred embodiment, thecatalytic substrate has a high melting point, low heat conductance,coefficient of thermal expansion, an ability to withstand thermal andvibrational shock, a low density, a high porosity, and a highpermeability.

In one embodiment, a first component of AETB is alumina fibers. Inpreferred instances of the present invention, the alumina (Al₂O₃ oraluminum oxide, e.g., SAFFIL), is typically about 95 to about 97 weightpercent alumina and about 3 to about 5 weight percent silica incommercial form. In other embodiments, alumina having a lower purity arealso useful, e.g., 90%, 92%, and 94%. In other embodiments, aluminahaving a higher purity are also useful. Alumina can be produced byextruding or spinning. First, a solution of precursor species isprepared. A slow and gradual polymerization process is initiated, forexample, by manipulation of pH, whereby individual precursor moleculescombine to form larger molecules. As this process proceeds, the averagemolecular weight/size increases, thereby causing the viscosity of thesolution to increase with time. At a viscosity of about ten centipoise,the solution becomes slightly adhesive, allowing fiber to be drawn orspun. In this state, the fiber may also be extruded through a die. Incertain embodiments, the average fiber diameter ranges from about one tosix microns, although larger and smaller diameter fibers are alsosuitable for the present invention. For example, the fiber diameters inother embodiments range from 1-50 microns, preferably 1-25 microns, morepreferably 1-10 microns.

In one embodiment, a second component of an AETB is silica fiber. Silica(SiO₂, e.g., Q-fiber or quartz fiber), in certain embodiments, containsover 99.5 weight percent amorphous silica with very low impurity levels.Silica of lower purities, e.g., 90%, 95%, and 97%, are also useful forthe invention. In certain embodiments, an amorphous silica is used thathas a low density (e.g., 2.1 to 2.2 g/cm³), high refractoriness (1600degrees Celsius), low thermal conductivity (about 0.1 W/m-K), and nearzero thermal expansion.

In one embodiment, a third component of an AETB is aluminaboriasilicafibers. In certain instances, aluminaboriasilica fiber(3Al₂O₃.2SiO₂.B₂O₃, e.g., NEXTEL 312) is typically 62.5 weight percentalumina, 24.5 weight percent silica, and 13 weight percent boria. Ofcourse, the exact percentages of the constituents of thealuminaboriasilica may vary. It is largely an amorphous product but maycontain crystalline mullite. Suitable aluminaboriasilica fibers andmethods of making the same are disclosed, for example, in U.S. Pat. No.3,795,524, the teachings of which are herein incorporated by referencein their entirety.

Another suitable material for use as a substrate of the presentinvention includes Orbital Ceramics Thermal Barrier (OCTB), availablefrom Orbital Ceramics (Valencia, Calif.).

Other suitable materials for use as a nSiRF-C in the present inventioninclude: AETB-12 (having a composition of about 20% Al₂O₃, about 12%(14% B₂O₃, 72% Al₂O₃, 14% SiO₂; NEXTEL™ fiber), and about 68% SiO₂);AETB-8 (having a composition of about 20% Al₂O₃, about 12% (14% B₂O₃,72% Al₂O₃, 14% SiO₂ NEXTEL™ fiber), 68% SiO₂); FRCI-12 (having acomposition of about 78% wt. silica (SiO₂), and 22% wt.aluminoborosilicate (62% Al₂O₃, 24% SiO₂, 14% B₂O₃); and FRCI-20 (havinga composition of about 78% wt. silica (SiO₂) and about 22% wt.aluminoborosilicate (62% Al₂O₃, 24% SiO₂, 14% B₂O₃).

In a preferred embodiment, the components of the inorganic fibersconsists, or consists essentially of, fibrous silica, alumina fiber, andaluminoborosilicate fiber. In this embodiment, the fibrous silicacomprises approximately 50-90 (%) percent of the inorganic fiber mix,the alumina fiber comprises approximately 5-50 (%) percent of theinorganic fiber, and the aluminoborosilicate fiber comprisesapproximately 10-25 (%) percent of the inorganic fiber mix. The fibersused to prepare the substrate of the present invention may have bothcrystalline and glassy phases in certain embodiments.

Other suitable fibers include aluminoborosilicate fibers preferablycomprising aluminum oxide in the range from about 55 to about 75 percentby weight, silicon oxide in the range from less than about 45 to greaterthan zero (preferably, less than 44 to greater than zero) percent byweight, and boron oxide in the range from less than 25 to greater thanzero (preferably, about 1 to about 5) percent by weight (calculated on atheoretical oxide basis as Al₂O₃, SiO₂, and B₂O₃, respectively). Thealuminoborosilicate fibers preferably are at least 50 percent by weightcrystalline, more preferably, at least 75 percent, and most preferably,about 100% (i.e., crystalline fibers). Sized aluminoborosilicate fibersare commercially available, for example, under the trade designations“NEXTEL 312” and “NEXTEL 440” from the 3M Company. Further, suitablealuminoborosilicate fibers can be made as disclosed, for example, inU.S. Pat. No. 3,795,524, which is incorporated herein by reference inits entirety.

Additional suitable fibers include aluminosilicate fibers, which aretypically crystalline, comprising aluminum oxide in the range from about67 to about 77, e.g., 69, 71, 73 and 75, percent by weight and siliconoxide in the range from about 33 to about 23, e.g., 31, 29, 27, and 25,percent by weight. Sized aluminosilicate fibers are commerciallyavailable, for example, under the trade designation “NEXTEL 550” fromthe 3M Company. Further, suitable aluminosilicate fibers can be made asdisclosed, for example, in U.S. Pat. No. 4,047,965 (Karst et al.), thedisclosure of which is incorporated herein by reference.

In other embodiments, the fibers used to prepare the substrate of thepresent invention comprise α-Al₂O₃ with Y₂O₃ and ZrO₂ additions, and/orα-Al₂O₃ with SiO₂ added (forming α-Al₂O₃/mullite)

Various specific materials can be used to prepare the catalyticsubstrate. In one embodiment, the material used to prepare a substrateof the present invention comprises, or alternatively consists orconsists essentially of, refractory silica fibers and refractoryaluminumborosilicate fibers. In another embodiment, the material used toprepare the catalytic substrate comprises refractory silica fibers,refractory grade alumina fibers, and a binding agent, preferably aboronoxide or a boron nitride powder. In another embodiment the fibersare high grade.

In another embodiment, the substrate comprises a refractory compositeconsisting essentially of aluminosilicate fibers and silica fibers in aweight ratio within the range of about 19:1 to 1:19, and about 0.5 to30% boron oxide, based on the total weight of the fibers. Alternatively,the weight ratio of aluminosilicate fibers to silica fibers is selectedfrom 16:1, 14:1, 12:1, 10:1, 8:1; 6:1, 4:1, 2:1, 1:1, 1:2, 1:4, 1:6,1:8, 1:10, 1:12, 1:14, and 1:16. The boron oxide is present in otherembodiments in about 5%, 10%, 15%, 20%, 25%, or 30%. In a furtherembodiment, the boron oxide and aluminosilicate fibers are present inthe form of aluminoborosilicate fibers. In a further embodiment, thecatalytic substrate comprises a nSiRF-C composite wherein thealuminosilicate fiber to silica fiber ratio ranges from 1:9 to 2:3 andthe boron oxide content is about 1 to 6% of the fiber weight.

In another embodiment, fibers suitable for preparing the substrate ofthe present invention include the refractory fibers produced by 3M suchas NEXTEL™ Ceramic Fiber 312, NEXTEL™ Ceramic Fiber 440, NEXTEL™ CeramicFiber 550, NEXTEL™ Ceramic Fiber 610, and NEXTEL™ Ceramic Fiber 720. Thecomposite grade fibers Nextel™ Fibers 610, 650, and 720 have morerefined crystal structures based on alpha-Al₂O₃ and do not contain anyglassy phases. This allows them to retain strength to highertemperatures than the industrial fibers. Nextel™ Fiber 610 hasessentially a single-phase composition of α-Al₂O₃. It has the loweststrength retention at temperature even though it starts with the higheststrength at room temperature. Both Nextel™ Fiber 650, which is α-Al₂O₃with Y₂O₃ and ZrO₂ additions, and Nextel™ Fiber 720 which is alpha-Al₂O₃with SiO₂ added (forming α-Al₂O₃/mullite) have better strength retentionat temperature and lower creep.

In another suitable embodiment, a nSiRF-C is made from or comprises (oralternatively, consists of or consists essentially of) ceramic fiberscomprising Al₂O₃, SiO₂, and B₂O₃, having the following attributes: 1)melting point of about 1600° C. to about 2000° C., preferably about1800° C.; 2) a density of about 2 to about 4 g/cc, preferably about 2.7to about 3 g/cc; 3) a refractive index of about 1.5 to about 1.8, morepreferably selected from 1.56, 1.60, 1.61, 1.67, and 1.74; 4) a filamenttensile strength (25.4 mm gauge) of about 100 to about 3500 MPa, morepreferably from about 150 to about 200 or from about 2000 to about 3000,or selected from 150, 190, 193, 2100, or 3100; 5) a thermal expansion(100-1100° C.) from about 2 to about 10, preferably about 3 to about 9,more preferably selected from 3, 4, 5.3, 6, and 8; 6) and a surface areaof less than about 0.4 m²/g, more preferably less than about 0.2 m²/g.In other embodiments, the crystal phase of the fibers are mullite andamorphous, substantially amorphous, γ-Al₂O₃, or amorphous SiO₂. In stillother embodiments, the dielectric constant of a fiber that is suitablefor use in preparing a substrate according to the present invention isabout 5 to about 9 (at 9.375 GHz), or preferably selected from the groupconsisting of 5.2, 5.4, 5.6, 5.7, 5.8, 6, 7, 8, and 9.

In certain embodiments, the substrate of the present invention issubstantially “shot-free” meaning free of particulate ceramic (i.e.,crystalline ceramic, glass, or glass-ceramic) from the fiber manufactureprocess.

In certain embodiments, the nSiRF C composite is “nonflexible.” In oneembodiment, nonflexible refers to a substrate that cannot be bent moreto an angle of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25 degrees(with respect to the point of bending) without breaking, cracking, orbecoming permanently deformed or misshaped.

The diameter of the fibers used different embodiments of the inventionmay vary. In certain embodiments, the average diameter is from about 1to about 50 microns, preferably 1 to about 20 microns. In otherembodiments, the average diameter is about 6, 7, 8, 9, 10, 11, 12, 13,14, or 15 microns. In other embodiments, the average fiber diameter foraluminiaboriasilica fibers is from about ten to about twelve microns.

In another embodiment, the catalytic substrate of the present inventionfurther comprises a binding agent such as boron nitride. In anotherembodiment of the present invention, boron nitride is added to replacethe aluminaboriasilica fiber when it is not used. That is, in someembodiments, the substrate comprises (or consists of or consistsessentially of or is made from) silica fiber, alumina fiber, and boronnitride in similar weight percentage as described above. In a furtherembodiment, the substrate comprises silica fiber, alumina fiber, and aboron binder. Each of these may, in certain embodiments, contain smallamounts of other material such as organic binders, inorganic binders andsome fibrous or non-fibrous impurities. In other embodiments, thesubstrate does not contain an organic binder. Furthermore, in otherinstances, the binder that is used to create the nSiRF-C is materiallychanged during the process of making, as is known in the art.

Additional suitable materials for use in preparing the substrate of thepresent invention are disclosed in U.S. Pat. No. 5,629,186 whichdescribes low density fused fibrous ceramic composites prepared fromamorphous silica and/or alumina fibers with 2 to 12% boron nitride byweight of fibers. In another embodiment, a thickening agent is added.Suitable thickening agents are known in the art.

In other embodiments, the ceramic fibers used to prepare the nSiRF-Chave an average tensile strength greater than about 700 MPa (100,000psi), preferably greater than about 1200 MPa (200,000 psi), morepreferably, greater than about 1800 MPa (300,000 psi), and mostpreferably, greater than about 2100 MPa (350,000 psi).

In another embodiment, a dispersant is added. Suitable dispersants areknown in the art.

In other embodiments, the catalytic substrate is treated with, altered,modified, and/or enhanced in one or more aspects as described hereinand/or as is known in the art.

In still other embodiments, minor impurities of various sources arepresent. In these cases, the impurities do not substantially affect thenSiRF-C and/or its attributes.

A substrate according to the present invention does not include aNEXTEL™ woven fabrics or mat.

Catalyst

In another aspect, the present invention is directed to a substrate asdescribed above comprising a catalyst. Any number of catalysts can beused with the substrate to form a catalytic substrate. The catalyst maybe coated onto the surface of the substrate. That is, the catalyst, inone embodiment, is adsorbed onto the surface (e.g., the walls of thechannels) of the catalytic substrate. Catalyst could also reside on theinside of the core of the substrate and attached to the individualfibers of the substrate. In certain embodiments, the present inventioncan function at the same or better levels compared to current technologybut require a smaller amount of catalyst.

In another embodiment, the catalyst is deposited only on the channelwall surfaces and not inside the channel walls. In another embodiment,the catalyst is deposited on the ingress channel walls, on the egresschannel walls, within the walls, or combinations thereof. In yet afurther embodiment, a first catalyst lines, coats, or permeates abeginning, or proximal, portion of the channel wall; a second catalystlines, coats, or permeates a middle portion of the channel wall; and yeta third catalyst at a terminal section of the channel wall.

In one embodiment, the catalytic substrate of the present inventionpreferably contains a catalytic metal. In another metal, the catalyticsubstrate does not contain a catalytic metal. However, under certainconditions, the substrate is able to catalyze suitable reactions withoutthe need for a separate catalytic metal, for example, in certainembodiments, a washcoat as described below may function as a catalyst.

Any catalyst capable of being applied to the substrate can be used. Sucha catalyst includes but is not limited to platinum, palladium (such aspalladium oxide), rhodium, derivatives thereof including oxides, andmixtures thereof. In addition, the catalysts are not restricted to noblemetals, combinations of noble metals, or only to oxidation catalysts.Other suitable catalysts include chromium, nickel, rhenium, ruthenium,silver, osmium, iridium, platinum, and gold, iridium, derivativesthereof, and mixtures thereof. Other suitable catalysts include binaryoxides of palladium and rare earth metals as disclosed in U.S. Pat. Nos.5,378,142 and 5,102,639, the disclosures of which are herebyincorporated herein by reference. These binary oxides may result fromthe solid state reaction of palladium oxide with the rare earth metaloxides, to produce, e.g., Sm₄PdO₇, Nd₄PdO₇, Pr₄PdO₇ or La4PdO₇. Othercatalysts that can be used in the present invention include thosedisclosed in U.S. Pat. No. 6,090,744 (assigned to Mazda MotorCorporation). Other suitable catalysts include non-metallic catalysts,organic catalysts, base metal catalysts, precious metal catalysts, andnoble metal catalysts.

Other suitable catalysts are disclosed in U.S. Pat. No. 6,692,712(assigned to Johnson Matthey Public Limited Company). Catalysts that donot comprise precious metals may be used in the present invention. Suchcatalysts are shown in U.S. Pat. No. 5,182,249.

Another suitable platinum catalyst developed by Engelhard is composed ofPt/Rh at 5:1 ratio (applied in an amount of about 5-150 g/ft³) and MgO(applied in an amount of about 30-1500 g/ft³).

In other embodiments, vanadium and derivates thereof, e.g., V₂O₅, areuseful catalysts, in particular for diesel particulate filters. Suchcatalysts have been used in commercially available in diesel particulatefilters.

Catalysts were developed that utilized vanadium compounds other thanV₂O₅, for example silver or copper vanadates. An example copper vanadatebase metal catalyst was developed by Heraeus (Strutz 1989). The catalystcan be prepared by doping and calcining copper vanadate Cu₃V₂O₈ withpotassium carbonate in the molar ratio Cu:V:K about 3:2:0.13. Thecatalyst loading was between 10 and 80 g/m² of the filtration surfacearea. Another suitable catalyst is Cu/ZSM5, which can be used as a DeNoxcatalyst.

Precious metals such as platinum, palladium, and rhodium are the mostcommon and are preferred, although other catalysts known in the art canbe used. These three precious metals have been known as excellent andhighly efficient catalysts with internal combustion engine emissions. Inover twenty-five years of catalytic converters, there has not reallybeen a meaningful substitute for this trinity. However, there arethousands of combinations of these catalysts configured according to theoriginal equipment manufacturer, vehicle, vehicle load, environmentalregulations, engine, transmission, etc. Throughout the truck andautomotive manufacturing industry, various combinations and formulationsof catalysts are employed. A catalytic substrate according to thepresent invention comprises any one or more of these catalystcombinations. Many combinations are considered proprietary material.Manufacturers such as Ford, GM, and Toyota have a unique catalystformula for each vehicle, due to the varying vehicle weights and engineperformance demands. Manufacturers also have different catalyst formulasfor the same vehicle depending upon where the vehicle will be sold orlicensed, e.g., Canada, United States, California, Mexico. Currently,these formulations may change two to three times per vehicle per modelyear, due to the strict governmental regulations. For these reasons,most manufacturers handle the application of the catalytic coatingsthemselves.

In a further embodiment, the catalytic substrate comprises a nSiRF C anda catalyst that is used in a commercially available catalyticenvironment.

In one aspect, once the substrate has been shaped to its finaldimensions and a washcoat is applied and cured, one or more catalystsare applied using known techniques and methods, such as the manner ofapplying a palladium-platinum based catalyst as disclosed in U.S. Pat.Nos. 5,244,852 and 5,272,125, the teachings of which are bothincorporated herein by reference in their entirety.

In one embodiment, the catalyst is in an amount sufficient for thecatalytic action to take place effectively. For example, the amountsufficient, in one embodiment, refers to an amount of catalyst, e.g., aprecious metal, interacting with and in the path of the emissionsufficient to react with as much of the emission as possible, such as80%, 85%, 90%, 95%, 97%, 98%, and 99%, and the like.

In one embodiment, the catalyst is deposited on or impregnated into thewashcoat, preferably as individual crystals. In this embodiment, thecatalysts are not applied as a veneer-like coating over the washcoat(like paint on a wall). When the catalysts are impregnated onto thewashcoat, they are applied so the end product is partially orsubstantially a colony of individual crystals. This can be visualized assalt crystals on a pretzel. It is preferable that sufficient spacing isprovided between the catalysts. At the same time, there should be enoughprecious metals in the fluid path, e.g., the exhaust path, at theoptimum catalytic activity operating temperature, i.e., light off, andthe precious metals must fit within the physical restraints, i.e.,space, permitted by the functionality and design of a vehicle andengine.

A manufacturing goal is to maximize the pollutants removed whileminimizing the amount of catalyst required on the substrate. Eachvehicle produces a different amount of pollutant, and as such, thesubstrate is in some embodiments customized to address that level ofpollutants and minimize the amount of precious metals.

In another embodiment, the catalyst addition to the catalytic substratecan occur during the slurry process when making of the substrate, or itcan occur after the machining process (as described below). In thiscase, the catalyst is mixed with the slurry of fibers prior to anyheating step.

Single and multiple catalyst formulations can be applied to a singlesubstrate, or due to the small size of the filter relative to theexisting catalytic converters and exhaust systems, the placement ofmultiple substrates is possible. Thus, the catalytic substrate of thepresent invention in one embodiment comprises or consists of or consistsessentially of one or more zones, wherein each zone has a differentcatalyst. Alternatively, one or more of the zones may be uncatalyzed.For example, a catalytic substrate of the present invention may includean oxidation catalyst in one zone which contains the front surface ofthe substrate, and a reducing catalyst in another zone which contain therear surface.

If the substrate is to be used as a flow through configuration, then itis preferable, although not required, for the catalysts, or the majorityof the catalysts, to reside along the surface of the channels. If thesubstrate is machined into a wall flow configuration, then it ispreferable for the catalysts to be evenly distributed throughout thesubstrate as the gases are going to be traveling through all of thesubstrate and not just passing through.

For example, the substrate of the present invention can be used in acatalyzed diesel particulate filters (CDPF). A CDPF utilizes catalystsdeposited directly on the substrate. Both precious and base metalcatalysts can be used, such as platinum, silver, copper, vanadium, iron,molybdenum, manganese, chromium, nickel, derivatives thereof (such asoxides) and others. Depending on the type of filter, the catalyst can beimpregnated directly into the media or an intermediate washcoat layercan be used. A CDPF can utilize exhaust temperatures of about 325-420°C. for regeneration, depending on engine technology (PM emissions) andfuel quality (sulfur content).

Platinum is one of the most active and most commonly used noble metalcatalysts, but palladium, rhodium, or ruthenium catalysts, usually inmixtures, are also suitable for use in the present invention. The listof common non platinum-group metals used in catalytic convertersincludes vanadium, magnesium, calcium, strontium, barium, copper andsilver. In one embodiment, platinum is the preferred catalyst for usewith diesel engines. In another embodiment, palladium and rhodiumsuitable for use with a gasoline engine.

Catalysts are typically quite expensive. It is therefore desirable toachieve the maximum reduction in pollution with the minimum amount ofcatalyst used. Platinum and palladium, two common catalysts, are bothexpensive precious metals. A substrate having a porous, permeable naturewith a large surface area on which catalysts can reside as evenlydistributed crystals or layer allow for achieving that objective. Anadvantage of the present invention is a lower amount of catalyst neededcompared to conventional substrates.

Typical platinum loadings in filters used for off-road engines throughthe 1990's were between 35 and 50 g/ft³. These filters, installed onrelatively high polluting engines, required minimum temperatures ofnearly 400° C. for regeneration. Later, when catalyzed filters wereapplied to much cleaner urban bus and other highway vehicle engines, itwas found that the catalyzed filters were able to regenerate at muchlower temperatures. However, higher platinum loadings were needed tosupport the low temperature regeneration. Filters used in clean engine,low temperature applications have typically platinum loadings of 50-75g/ft³.

In one embodiment, the catalytic substrate comprises a catalyst in theamount of about 1 to about 100, about 1 to about 50, about 1 to about30, or about 10 to about 40 g/ft³.

In another embodiment, the catalytic substrate, preferably an nSiRF-Csuch as AETB, OCTB, and FRCI, comprises catalyst of platinum and rhodiumin a ratio of about 5:1 and an amount of about 30 g/ft³.

Filtering Substrate

The present invention is directed to a catalytic substrate comprising anon-woven Sintered Refractory Fibrous Ceramic (nSiRF-C) composite, asdescribed herein, that can be used in particulate filters, and relateddevices. The filtering substrate is fashioned into particular shapes,designs, sizes, and configurations that are useful for filtering, inparticular for filtering particulate matter. The filtering substrate isparticularly useful for filtering particulate matter under extremeconditions (temperature, pressure, etc), such as filtering a flow ofexhaust gas. The filtering substrate can be used in additionalapplications in which the filtering of small particulate matter isrequired.

In one embodiment, the filtering substrate comprises, or alternativelyconsists of or consists essentially of, a nSiRF-C composite as describedabove for the catalytic substrate. The filtering substrate does notcontain a catalyst. All variations, embodiments, and examples ofmaterials suitable for use as the substrate of a catalytic substrate arelikewise suitable for the filtering substrate of the present invention.

The filtering substrate is shaped into configurations suitable for usesdescribed herein, in particular for use in particulate traps such asdiesel particulate traps and diesel particulate filters.

In one embodiment, a filtering substrate of the present invention isalumina enhanced thermal barrier (“AETB”) material or a like materialknown to one of ordinary skill in the art. AETB is made fromaluminaboriasilica (also known as alumina-boria-silica,aluminoborosilicate, and aluminoboriasilicate) fibers, silica fibers,and alumina fibers. One commonly known application for AETB is as anexterior tile on the Space Shuttle, ideal for shuttle re-entry. Theattributes that make AETB unique and desirable to the space industry arealso preferred in organic combustion technology. AETB has a high meltingpoint, low heat conductance and coefficient of thermal expansion,ability to withstand thermal and vibrational shock, low density, andvery high porosity and permeability.

The filtering substrate of the present invention is optionally treatedwith one or more chemical additives.

In another embodiment, the present invention is directed to a dieselparticulate trap comprising a filter as described herein without anycatalyst applied to it.

In another embodiment, the present invention is directed to a dieselparticulate trap comprising a filter as described herein in combinationwith a CRT® diesel particulate trap (NOX, HC adsorbers).

In another embodiment, the present invention is directed to a dieselparticulate trap comprising a filter as described herein in combinationwith SCR.

In another embodiment, the filtering substrate comprises a plurality ofchannels as described in more detail below. Furthermore, the filteringsubstrate can be modified, altered, and/or enhanced in one or moreaspects as described herein and/or as known in the art.

Attributes of a Catalytic and Filtering Substrates

The present invention has one or more, preferably at least three, four,five, six, seven, eight, nine, or ten, attributes which are advantageousover conventional catalytic or filtering substrates.

Suitable for Use

The invention is directed in certain embodiments to a catalyticsubstrate or filtering substrate comprising nSiRF-C and a catalyst,suitable for use in a catalytic converter. The substrate is suitable foruse in any number of catalytic converters, filtering devices andapplications thereof.

For example, the catalytic substrate and filtering substrate of thepresent invention is suitable of use in any of the applicationsgenerally used for prior art substrates. Suitable uses include, but arenot limited to, the use of a substrate of the present invention in anexhaust system any 1) Mobile On-Road Engines, Equipment, and Vehicles,including cars and light trucks; highway and street motorcycles,three-wheeled motorcycle (e.g., motorized tricycles, autorichshaws),motorized tricycles; heavy-duty highway engines, such as trucks andbuses; 2) Mobile Non-Road Engines, Equipment, and Vehicles, includingcompression-ignition engines (farm, construction, mining, etc.); smallspark-ignition engines (lawn mowers, leaf blowers, chainsaws, etc.);large spark-ignition engines (forklifts, generators, etc.); marinediesel engines (commercial ships, recreational diesel, etc.); marinespark-ignition engines (boats, personal watercraft, etc.); recreationalvehicles (snowmobiles, dirt bikes, all-terrain vehicles, etc.);locomotives; aviation (aircraft, ground support equipment, etc.); and 3)Stationary Sources, including hundreds of sources, such as power plants,refineries, and manufacturing facilities.

In another embodiment, a catalytic substrate of the present invention issuitable for use in a particular vehicle if the substrate as describedherein, when a part of a catalytic converter, functions so that thevehicle meets the emissions standards of any one of 1990, 2007, and2010, as defined by the EPA.

In another embodiment, the catalytic substrate catalyzes the reaction ofpollutants to nonpollutants at a high level. For example, the conversionof pollutants to nonpollutants is catalyzed at an efficiency of greaterthan 50%. In another embodiment, the conversion of pollutants tononpollutants is catalyzed at an efficiency of greater than 60%. Instill other embodiments, the conversion rate is selected from the groupconsisting of 70%, 80%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%,99%, and 99.9%. In certain embodiments, the conversion rate refers tothe total conversion of non-particulate pollutants. In otherembodiments, the conversion rate refers to the conversion of specificnon-particulate pollutants, e.g., NOx to N₂, CO to CO₂. or HCs to CO₂and H₂O. In other embodiments, the conversion rate refers to thepercentage of particulate matter removed from an exhaust gas.

In another embodiment, a catalytic substrate of the present invention issuitable for use in a particular application if the catalytic substratepasses certain OEM-prescribed and preferred tests, such as U.S. FederalTest Protocol 75 (U.S. FTP75). Such tests are known in the art. (See forexample Document No. EPA420-R-92-009, published by the U.S. EPA,available at http://www.epa.gov/otaq/inventory/r92009.pdf, which isherein incorporated by reference in its entirety). Additionally, as aback-cat or DPT in retrofit applications, EPA and/or state/localagencies may have to approve of the products for use, including thesubstrate contained therein.

Surface Area

The available surface area of a substrate is an important characteristicof filtering substrate or catalytic substrate. One characteristic of asuitable substrate for a catalytic converter is for it to have a highgeometric surface area (GSA). The high GSA allows for maximum reactionprobability.

A large open frontal area (OFA) allows for greater amount of gas to passthrough without obstructing its flow and causing back-pressure. Openfrontal area (OFA) is defined as the part of the total substratecross-section area which is available for the flow of gas (i.e., thecross-section area of the filter inlet channels). It is typicallyexpressed relative to the total substrate cross-section.

An attribute of the substrate of the present invention is its highsurface area or high GSA. The surface area of the substrate is animportant characteristic for catalysis application. Surface area is thesum amount of surface that exhaust emissions must pass across whentraveling through an exhaust filter. Increased surface area translatesinto an increased surface for chemical reactions to take place betweenpollutants and catalytic and thermal processes, making a catalyticconverter process quicker and more efficient. Speed and efficiency canresult in little to no clogging, which can cause failure of the exhaustsystem. Furthermore, the increased surface area of the substrate ofcertain embodiments also includes increased filtering efficiency and/orcapability.

Geometric surface area is the total surface area that precious metalscan be impregnated onto in one cubic inch. A substrate having a highgross surface area is preferred. Certain embodiments of the presentinvention have a much higher geometric surface area that can beimpregnated with catalyst, compared to conventional substrates, such ascordierite and SiC.

Gross wall volume is the total amount of wall volume that exists in aone inch cube of configured substrate. Gross wall volume is calculatedas each wall surface area multiplied by each respective thickness andsummed. A substrate having a lower gross wall volume is preferred. Incertain embodiments, the gross wall volume of the substrate of thepresent invention is lower than that of conventional substratematerials, such as cordierite and Sic.

In certain embodiments, the gross wall volume of the catalytic substrateis from about 0.5 to about 0.1, from about 0.4 to about 0.2, or about0.3 in³/in³ (cubic inches per cubic inch). In a preferred embodiment,the gross wall volume substrate is about 0.25 to about 0.28, morepreferably about 0.27, more preferably about 0.272 in³/in³.

Due to the lower gross wall volume of the present invention in certainembodiments, a lower amount of catalyst, such as palladium, is needed toperform the catalytic action with the present invention than acordierite of a similar size.

Porosity and Permeability

Pore attributes also affect mechanical and thermal attributes of thesubstrate. A trade-off can exist between porosity and mechanicalstrength: substrates of smaller pore size and lower porosity arestronger than those of higher porosity for certain conventionalsubstrates. Thermal attributes, both specific heat capacity and thermalconductivity may decrease with increasing porosity in certain materials(Yuuki 2003).

The first wall-flow monoliths, introduced in the late 1980's, hadchannels as large as 35 μm in diameter. In order to maximize filtrationefficiency, channels were made smaller, typically in the range of 10-15μm in filters used in the 1990's. In the development of new materials,filter manufacturers differentiate their target pore attributes,primarily in consideration of the catalyst system to be applied (Ogyu,K., et al., 2003. “Characterization of Thin Wall SiC-DPF”, SAE2003-01-0377; Yuuki, K., et al., 2003, “The Effect of SiC Properties onthe Performance of Catalyzed Diesel Particulate Filter (DPF),” SAE2003-01-0383). The applications can be classified as follows:

Non-catalyzed filters, such as those used in fuel additive regeneratedsystems: The main requirement is a high soot holding capacity. Certainconventional filters have a porosity that is about 40-45% with poresbetween 10-20 μm.

Catalyzed filters, such as those in passively regenerated systemsrequire more porosity and possibly larger pore size to enable coatingwith increasingly more complex catalyst systems (as opposed to thesimple catalysts used in the 1990's, which often had very little or nowashcoat material). The substrates should have acceptably low pressureloss after being coated with catalyst/washcoat systems at about 50 g/dm³loading. Certain prior art filters have a porosity of about 45-55%range. Additional heaters may also be applied.

Filter/NOx adsorber devices, such as the DPNR system or CRT (continuousregeneration trap) incorporate NOx storage/reduction systems and requirehigh washcoat loadings, possibly above 100 g/dm³. Certain prior artsubstrates have a porosity of about 60% (a 65% porosity substrate hasbeen reported, with mechanical strength being the main limitation inincreasing porosity (Ichikawa, S., et al., 2003, “Material Developmentof High Porous SiC for Catalyzed Diesel Particulate Filters,” SAE2003-01-0380).

Another attribute of certain embodiments of the catalytic or filteringsubstrate of the present invention is its high porosity. In certainembodiments, the porosity of a substrate of the present invention isfrom about 60%, 70%, 80%, or 90%. In other embodiments, the substratehas a porosity of about 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%(expressed as a percent of pore space relative to the solid substrate).

In one embodiment, the porosity of an exemplary embodiment of thepresent invention is approximately 97.26%. By comparison, cordierite isabout 18-42%. In this embodiment, the material of the present inventiononly has about 2.74% material to obstruct the flow of exhaust gas. Thisfine web of material actively catches the particulate and burns it offvery effectively. Due to the trapping of particulates in depthfiltration mode and not only along channel walls, considerable PMbuildup does not occur under situation where regeneration time is longerthan PM build-up time. High porosity translates into better and moreeffective interaction between pollutants and the catalyzed ornon-catalyzed substrate surface. At the same time, gas flow buildup canbe released laterally as well as along the intended gas flow direction.

Referring to FIGS. 22 a and 22 b, an exemplified substrate 2200, 2205 ofthe present invention is shown. Substrate 2200, 2205 is approximatelyninety-seven percent porous. As compared to the samples of cordierite inFIGS. 2 a and 2 b and silicon carbide in FIG. 3, all being substantiallythe same scale, substrate 1200, 1205 is more porous and less dense. InFIG. 22 b, particular matter PM-10 2210 and PM-2.5 2225 is illustratedto scale. The particulate matter PM-10 2210 and PM-2.5 2225 can easilypermeate the fibers of substrate 2205, as compared to the cordieritesample 205 exemplified FIG. 2 b. Also, compared to the silicon carbide300 of FIG. 3, the density of silicon carbide is about thirty to fiftytimes that of substrate 2200, 2205.

The higher porosity in certain embodiments of the present inventionprovides a higher surface area and lowers the backpressure. As a result,the present invention is more efficient at NOx reduction, hydrocarbonand CO oxidation, and particulate matter trapping.

Pore characteristics, including volume percent porosity, sizedistribution, structure, and interconnectivity determine the monolithability to filter particulates. Additionally, if gas molecules candiffuse into a porous substrate, the probability of a catalytic reactionincreases dramatically. Together with the cellular geometry, porositycharacteristics also influence the monolith's hydraulic resistance toflow and the pressure drop. Some attributes which are desired for highfiltration efficiency (e.g., low porosity and small pore size) areopposite to those required for low pressure drop. Others, such as goodpore interconnectivity and absence of closed, “dead end” pores, aredesired for both low pressure drop and high efficiency. The substratesof the present invention in another embodiment provide both highfiltration efficiency and low pressure drop.

Emissivity and Heat Conductance

Another property of substrates used in catalytic converters andparticulate filters is emissivity. Emissivity is the tendency toemission heat; comparative facility of emission, or rate at whichemission takes place, as of heat from the surface of a heated body.

An ideal substrate takes into consideration the temperature that (1) thefastest ramp-up to high conversion efficiency; (2) is safest fromthermal harm (e.g., due to thermal shock or due to high-temperaturemelting/cracking of substrate); (3) uses a minimal amount of auxiliaryenergy; and (4) is inexpensive to produce. Increasing temperaturerequires additional energy and expense. Further, certain amounts of theenergy source are conducted, drawn, or channeled away through thermalconductivity.

Emissivity is a ratio of reflectance with values between 0 and 1, withone being perfect reflection. Different substrates used for catalyticconverters and particulate filters have different emissivity values.High emissivity allows the catalyst substrate to minimize heat transferout of the system, thereby heating the air inside the catalyticconverter or particulate filter faster. The emissivity is a measure ofthe heat reflectance property of the material and a high value isdesirable.

In certain embodiments, a substrate of the present invention preferablyhas an emissivity of about 0.8 to 1.0. In another embodiment, theemissivity of the substrate of the present invention is about 0.82,0.84, 0.86, 0.88, and 0.9. Further suitable values for emissivity of asubstrate of the present invention include 0.81, 0.83, 0.85, 0.87, and0.89. In other embodiments, the emissivity is about 0.9, 0.92, 0.94,0.96, or 0.98. Reflectivity of heat allows the gaseous material in thepores to heat up much faster since little heat is retained by thesubstrate material itself. That results in quicker lightoff and littletemperature rise of the outside surface of the substrate.

The thermal conductivity of a material is the quantity of heat thatpasses in unit time through unit area of a plate, when its oppositefaces are subject to unit temperature gradient (e.g., one degreetemperature difference across a thickness of one unit). Thermalconductivity has the units of Watts of energy per meter thick and Kelvinchanged (W/m-K). In preferred embodiments, the substrate of the presentinvention have a low thermal conductivity. For example, in oneembodiment, the thermal conductivity of a substrate of the invention isless than about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9. Inanother embodiment, the thermal conductivity of a substrate of theinvention is less than about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07,0.08, or 0.09. In another embodiment, the thermal conductivity of asubstrate of the invention is from about 0.1 to about 0.01, from about0.2 to about 0.02, from about 0.3 to about 0.03, from about 0.4 to about0.04, from about 0.5 to about 0.05, from about 0.6 to about 0.06, fromabout 0.7 to about 0.07, from about 0.8 to about 0.08, or from about 0.9to about 0.09. In another embodiment, the thermal conductivity of thepresent invention is approximately 0.0604 W/m-K.

By comparison, a sample of cordierite is about 1.3 to 1.8 W/m-K. Theseresults indicate that, by way of example of a particular embodiment, if1000 Watts of heat energy is lost from a given volume of cordieritematerial, only 33 Watts would be lost from the same volume of thematerial from the present invention. Thus, the material of the presentinvention has a thermal conductivity thirty times greater thancordierite.

Additionally, in other embodiments, the process of preparing thesubstrate further comprises preparing a catalytic substrate or filteringsubstrate further comprising an emissivity enhancing agent, said processcomprising applying an emissivity enhancing agent to said substrate,preferably to a nSiRF-C, more preferably an AETB, OCTB, or FRCImaterial. Other preferred substrates include any of the specificsubstrates disclosed herein. In further embodiments, the catalyticsubstrate further comprises an emissivity enhancing agent and a catalystselected from the group consisting of palladium, platinum, rhodium,derivatives thereof, and mixtures thereof. Other physical and chemicalmodifications as described herein can be applied to such embodiments.Emissivity enhancing agents are known in the art.

Thermal Attributes

A substrate having a low coefficient of thermal expansion allows for thesubstrate to withstand rapid changes in temperature without significantexpansion or contraction. A suitable coefficient of thermal expansionalso allows for the substrate to expand with heat at the same rate asthe protective matting around it and the canister.

It is also preferable for the substrate material to withstand a highrange of temperatures so that it does not cause a catalytic converter orparticulate filter meltdown if the temperature rises to a high value,for example, during occasional fuel burning. Additionally, if thesubstrate material can withstand high temperatures, the catalyticconverter or filter can be placed closer to the engine.

Related properties include low thermal mass and heat capacity. Amaterial that has a low thermal heat mass and heat capacity allows forless heat energy to be wasted in raising the temperature of the catalystsubstrate. If the catalyst substrate heats up quickly, more of the heatenergy coming via the exhaust gas is used to trigger the light-off ofthe catalyst components.

Thermal conductivity is the capability of the material to conduct heatas a consequence of molecular motion. More specifically, thermalconductivity is also a measure of the quantity of heat that passes inunit time through unit area of a plate whose thickness is unity, whenits opposite faces differ in temperature by one degree. The more amaterial conducts heat, the more energy is needed to overcome loss andreach the required temperature. Preferably, a material reflects heat,rather than conducts. A lower thermal conductivity value is preferred somore heat energy is utilized in the pore spaces and not lost from theabsorption by the substrate. The chemistry of different substancesdetermines the level of thermal conductivity. Additionally, the thermalconductivity of the filter medium is a major influence on the efficiencyof an exhaust emission filter, since loss of temperature negativelyimpacts reactivity. A low thermal conductivity is preferred because moreof the heat energy generated is reflected back at the particulates, andwill remain in the pore space. In other words, the lower the thermalconductivity, the lower the loss of heat. Lower heat loss translatesinto less energy needed to obtain the desired temperature range forcatalytic conversion and higher energy efficiency.

Specific heat is the heat in calories required to raise the temperatureof one gram of a substance one degree Celsius. A substrate with a highspecific heat will reflect ambient heat, e.g., from an exhaust or anauxiliary source, back into the pore space where combustion or catalyticreduction and oxidation processes require the heat. For instance, underextreme conditions, e.g., the Arctic, it will take longer to heat up alow specific heat filter and cool hot filters, increasing the chance forexternal heat damage. A lower specific heat is preferable because isreaches operating temperature faster and with less energy.

In certain embodiments, a substrate of the present invention has anumber of preferred thermal attributes. Preferably, the material is suchthat heating of the air in the pore space occurs preferentially comparedto the heating of the substrate. Preferably, the substrate of thepresent invention has a high melting point, and in certain embodiments,a higher melting point than conventional substrates. A high meltingpoint is preferred, in part, due to the extreme temperatures to which acatalytic substrate or filtering substrate is exposed.

In a preferred embodiment, a substrate of the present inventionpreferably has a high melting point. In one embodiment, the meltingpoint is greater than about 1500° F. In another embodiment, the meltingpoint is greater than about 2000° F. In another embodiment, the meltingpoint is greater than about 2500° F. In a further embodiment, themelting point of the substrate is about 2000 to about 4000° F. In afurther embodiment, the melting point of the substrate is about 3000 toabout 4000° F. Other suitable melting point ranges include from about3000 to about 3100, from bout 3100 to about 3200, from about 3200 toabout 3300, from about 3300 to about 3400, from about 3400 to about3500, from about 3500 to about 3600, from about 3600 to about 3700, fromabout 3700 to about 3800, from about 3800 to about 3900, and from about3900 to about 4000. In another preferred embodiment, the substrate has amelting point of approximately 3632 degrees Fahrenheit.

In one embodiment of the present invention, the substrate has a meltingpoint of approximately 3,632 degrees Fahrenheit. For example, if avehicle is situated in below freezing temperatures, a blast of 1,500degree Fahrenheit exhaust fumes will not cause the substrate to crack orfracture. Similarly, certain embodiments of the substrate will notoverheat and crack. Certain samples of cordierite have a melting pointof about 1,400 degrees Celsius.

The specific heat of an exemplary embodiment of the present invention isapproximately 640 J/kg-K (Joules per kilogram-Kelvin). A sample ofcordierite is about 750 J/kg-K. Even though the cordierite has a greaterspecific heat, cordierite filters have a greater mass to heat up. Theresult is more heat energy is needed to reach operating temperaturemaking the cordierite less efficient.

A multiple use temperature limit is the maximum temperature in which asubstance can be subjected a plurality of times without substantialdegradation. The higher the temperature a substrate can continue tooperate without micro-fractures or spallation, the less chance of thesubstrate breaking or cracking over time. This in turn means thesubstrate is more durable over a wider temperature range. A highermultiple use temperature limit is preferred. A suitable multiple usetemperature limit for certain embodiments of the catalytic or filteringsubstrates of the present invention is one selected from the groupconsisting of about 2000° C., 2100° C., 2200° C., 2300° C., 2400° C.,2500° C., 2600° C., 2700° C., 2800° C., 2900° C., 3000° C., and 3100° C.

The multiple use temperature limit of an exemplary embodiment of thepresent invention is 2,980 degrees Celsius. A sample of cordierite isabout 1,400 degrees Celsius. The embodiment of the present invention canwithstand more than twice the temperature than cordierite beforebreaking down. This permits the material to function in a greater rangeof exhaust environments.

The coefficient of thermal expansion is a ratio of the increase of thelength (linear coefficient), area (superficial), or volume of a body fora given rise in temperature (usually for zero to one degree Celsius) tothe original length, area, or volume, respectively. These threecoefficients are approximately in the ratio 1:2:3. When not specificallyexpressed, the cubical coefficient is usually intended. The less asubstrate will expand when heated, the less chance of leaking,fracturing, or damage to filter assembly. A lower thermal expansion ispreferred to ensure that the substrate keeps its dimensions even whenheated or cooled.

The coefficient of thermal expansion for an exemplary embodiment of thepresent invention is approximately 2.65×10⁻⁷ W/m-K (Watts per meterKelvin). A sample of cordierite is about 2.5×10⁻⁶ W/m-K to 3.0×10⁻⁶W/mK. The thermal expansion of a material of the present invention isless than ten times that of cordierite.

The coefficient of thermal expansion of the substrate is preferablycompatible with the coefficient of thermal expansion of any washcoat.

In one embodiment, a catalytic or filtering substrate of the presentinvention, compared to certain prior art substrates such as cordierite,has an increased resistance to damage by thermal or mechanical stress;has a lower risk of clogging with soot and/or ash; is more tolerant toadditive ash accumulation when used with fuel additive regeneration; andhas good efficiency for particle number reduction.

Density

When considering substrates to be used in catalytic converters or dieselparticulate filters, it is preferable to use a substrate that has a lowdensity. The material having a low density reduces the weight of thesubstrate and hence the overall weight of the vehicle. Furthermore, lowdensity is complimentary to high porosity and permeability

Higher density translates into a higher weight. Weight is a large factorpertaining to any engine in motion. The heavier the part, the moreenergy is needed to move it. In order for these filters to accommodatethe increased volume of particulate generated by a engine, the filtersizes have to increase, which adds to vehicle weight and manufacturingand operating costs. Thus, a lower density material is desired. Ofcourse, the density is not so low that structural integrity isinsufficient.

Another attribute of the substrate of the present invention is itsdensity. The density of the substrate is lower than that of certainconventional filters and substrates used for filtering and as catalyticsubstrate. Density is the ratio of mass of a portion of matter to itsvolume. Greater density requires more energy to reach operatingtemperature. In other words, more energy is needed to heat up a densematerial than a less dense material. For materials with the samespecific heat, greater density directly translates into greater weightfor set volume. Weight is detrimental to a vehicle's mileage andperformance, as the engine must work harder to move heavier equipment.Increased density also translates into more heat required to achieve theproper temperature for catalytic activity or “light off” to occur. Thedensity of some materials currently used as substrates or filters arehigher than optimal. For example, a sample of cordierite is about 2.0 to2.1 g/cm³. Thus, there is a need for a substrate and a filter having alower density. The density of the substrate of the present invention islower than that of cordierite.

In one embodiment, the catalytic substrate of the present inventionpreferably has a low density. The density of the substrate of thepresent invention may be in the range from about 2 to about 50 poundsper cubic foot (lb/ft³). In a preferred embodiment, the density of thesubstrate is in the range of about 5 to about 30 pounds per cubic foot,more preferably, from about 8 to 16 pounds per cubic foot. Otherpreferred embodiments include catalytic substrate that has a density ofabout 8, 9, 10, 11, 12, 13, 14, 15, or 16 lb/ft³. A low density thatstill imparts structural integrity is preferred.

In one embodiment, the substrate of the invention has a density of about8 lbs/ft³ and 22 lbs/ft³, preferably from about 8 lbs/ft³ and 22lbs/ft³. In another embodiment, the substrate comprises AETB-8 orAETB-16, having densities of about 8 lbs/ft³ and about 16 lbs/ft³respectively. Other suitable densities include a density selected fromabout 9, 10, 11, 12, 13, 14, 15, and 16 lbs/ft³.

In another embodiment, the density of the substrate is approximately0.10 to approximately 0.25 g/cm³ (grams per cubic centimeter).

Structural Integrity

The structural integrity of the substrate material is a characteristicthat is important to consider. Structural integrity refers to thematerial's ability to withstand vibrational and mechanical stresses,i.e., shake and bake. For example, substrate strength is important forwithstanding packaging loads and subsequent use in the engine exhauststream with the related exposure to various stresses, including enginevibrations, road shock, and temperature gradients. High-strengthsubstrates are desirable for robust catalytic converter systems andparticulate filters. The strength of the substrate material may becontrolled by the type of intra- and intercrystalline bonding, theporosity, pore size distribution, and flaw population. Additionally,substrates can be strengthened by the application of chemical/materialcoatings on the inside of outside. The strength of the cellularstructure of the substrate may further determined by its dimensions,cross-sectional symmetry, and its cellular attributes, such as celldensity, channel geometry, and wall thickness. Substrate strength mustexceed the stress to which the material is exposed during both packagingand operation. If the stress exceeds the strength, the substrate willcrack.

Structural integrity of a material may be measured by the material'stensile modulus. Tensile modulus is a material's resistance to rupture.Specifically, the greater longitudinal stress a material can bearwithout tearing asunder. Tensile modulus is usually expressed with areference to a unit area of cross section, the number of pounds persquare inch, or kilograms per square centimeter necessary to producerupture. Tensile modulus is relevant in whether the substrate canwithstand the force generated by violent, exhaust gas flow pressure.

Additionally, a substrate should have a good coatability so that thewashcoat and/or a catalytic coat can be applied to the substrate.Likewise, the substrate should have washcoat compatibility, allowing forthe catalysts to mount well onto the substrate so that catalysts are notdisplaced from their location during normal wear and tear of the system.Good coatability and washcoat compatibility also enhances the long-termeffectiveness of the catalytic converter system. Good coatability andwashcoat compatibility also increases the lifetime of the catalyst.

Another attribute of the substrate of the invention is its structuralintegrity. Structural integrity of a material may be measured by thematerial's tensile modulus. Tensile modulus is a material's resistanceto rupture. Specifically, the greater longitudinal stress a material canbear without tearing asunder. Tensile modulus is usually expressed witha reference to a unit area of cross section, the number of pounds persquare inch, or kilograms per square centimeter necessary to producerupture. Tensile modulus is relevant in whether the substrate canwithstand the force generated by violent, exhaust gas flow pressure.

A catalytic substrate according to the present invention preferably hasa higher tensile modulus. For example, in one embodiment, the substrateof the present invention has an axial strength of about 2.21 MPa. Ofcourse, higher axial strengths are suitable as well. Other suitablevalues include 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 MPa.

Furthermore, structural integrity of the catalytic substrate of theinvention is such that it can withstand the conditions encounteredduring its use in a catalytic converter in commercial vehicles.

In another embodiment, the substrate of the invention, e.g., nSiRF-C,preferably has a high structural integrity and a low density.

Reduction of Pollutants

The substrate plays an important role in enhancing the catalyticactivity of the catalyst materials coated on it. Additionally substratesare used to trap particulate material which is then burnt off asvolatile gases.

Another advantage of the substrate of the present invention is itsincreased ability to reduce the amount of pollutants in an exhaust gas.The present invention has enhanced catalytic and filtering capabilitiesas compared to certain conventional technologies.

In certain embodiments, the substrate of the present invention iscapable of reducing CO emission from an exhaust gas by at least about50%. In one embodiment, the substrate of the present invention iscapable of reducing CO emission from an exhaust gas by at least about60%, 70%, 80%, or 90%. In another embodiment, the substrate is capableof reducing CO emission by at least 91%, 92%, 93%, 94%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, or 100%.

In certain embodiments, the substrate of the present invention iscapable of reducing NOx emission from an exhaust gas by at least about50%. In one embodiment, the substrate of the present invention iscapable of reducing NOx emission from an exhaust gas by at least about60%, 70%, 80%, or 90%. In another embodiment, the substrate is capableof reducing NOx emission by at least 91%, 92%, 93%, 94%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, or 100%.

In certain embodiments, the substrate of the present invention iscapable of reducing HC emission from an exhaust gas by at least about50%. In one embodiment, the substrate of the present invention iscapable of reducing HC emission from an exhaust gas by at least about60%, 70%, 80%, or 90%. In another embodiment, the substrate is capableof reducing HC emission by at least 91%, 92%, 93%, 94%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, or 100%.

In other embodiments, the substrate of the present invention is capableof reducing VOC emission from an exhaust gas by at least 50%. In oneembodiment, the substrate of the present invention is capable ofreducing VOC emission from an exhaust gas by at least about 60%, 70%,80%, or 90%. In another embodiment, the substrate is capable of reducingVOC emission by at least 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%,99.5%, 99.9%, or 100%.

In other embodiments, the substrate of the present invention is capableof reducing PM-10 emission from an exhaust gas by at least 50%. In oneembodiment, the substrate of the present invention is capable ofreducing PM-10 emission from an exhaust gas by at least about 60%, 70%,80%, or 90%. In another embodiment, the substrate is capable of reducingPM-10 emission by at least 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%,99.5%, 99.9%, or 100%.

In other embodiments, the substrate of the present invention is capableof reducing PM-2.5 emission from an exhaust gas by at least 50%. In oneembodiment, the substrate of the present invention is capable ofreducing PM-2.5 emission from an exhaust gas by at least about 60%, 70%,80%, or 90%. In another embodiment, the substrate is capable of reducingPM-2.5 emission by at least 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%,99.5%, 99.9%, or 100%.

Reduced Weight

It is a goal of the vehicle manufacturers to reduce the overall weightof the vehicle to improve its fuel economy and engine efficiency. Heavysubstrates add un-necessary weight to the vehicle. Additionally, ifsubstrates are not efficient enough in reducing pollution, more than onesubstrates may be required to play in line to reach target pollutionlevels. This greatly enhances the overall weight of the vehicle.

Additionally, current catalytic converters require the use of additionaldevices which are often heavy and clunky. Some of these devices, such asheat shields and particular matting, are used to deal with thetemperature of the catalytic converter. Others, such as oxygen sensors,are required to meet certain government regulations.

In certain embodiments of the present invention, the catalytic substrateor filtering substrate has reduced weight in comparison to aconventional catalytic or filtering substrates. This is due, in part, tothe lower density of the substrate of the present invention compared tocertain conventional substrates. Alternatively, the lower weight may bedue to the need for a smaller amount of catalytic or filtering substratebecause of the improved filtering and catalytic function of someembodiments of the present invention compared to conventionaltechnologies. A lower weight of a catalytic or filtering substrate has anumber of benefits. For example, a lower weight of a substrate maytranslate into improved fuel efficiency for vehicles. Furthermore, alower weight would translate into easier to handle and possible saferhandheld engine devices.

In a preferred embodiment, the exterior surface of the substrate doesnot heat up to the same extent as conventional catalytic convertersubstrates during use. In some embodiments, the need for a heat shieldand/or insulation is reduced.

Acoustical Attributes

Acoustic attenuation may be defined as either the diminution ofthickness, thinness, emaciation; diminution of density; diminution offorce or intensity; or weakening of acoustic energy (sound). In oneembodiment of the present invention, the acoustic attenuation is thesubstrate's ability to attenuate or dampen acoustic energy in engineexhaust. A substrate of the present invention can replace or complimentan engine's muffler assembly, as disclosed herein, thus decreasingexhaust noise and exhaust system costs. A higher acoustic attenuation ispreferred.

In another embodiment the porosity, density and size of the substratemay be varied to ‘tune’ the acoustical attenuation for desiredapplications.

In another embodiment, the acoustical attenuation of the substrate maybecoupled with standard metal-muffler based techniques to dampen and/or‘tune’ the sound existing the exhaust system.

Type of Flow

Flow-through

In one aspect, the substrate is structured for a flow-through use. Theflow-through configuration is known in the art. In one embodiment, thechannels (or pores) are essentially aligned parallel to each otheracross the entire length of the substrate. Gas flow enters the substrateat one end and runs down the through the channels through the entirelength of the substrate to exit on the other side.

Any number of flow-through configurations are useful and suitable forthe catalytic substrate of the present invention. Flow throughconfigurations that are known in the art can be applied to the catalyticsubstrate of the present invention.

In one embodiment, the flow through configuration comprises a pluralityof substantially parallel channels that extend fully through the lengthof the substrate.

In another embodiment, the walls of the channels are not parallel to thelateral or surface of the substrate.

Wall-flow

Another embodiment of the invention is a catalytic substrate orfiltering substrate of the present invention configured in the wall flowconfiguration. It has been surprisingly determined that a catalyticsubstrate comprising an nSiRF-C of the present invention can beconfigured in the wall flow configuration.

In another aspect of the invention, the substrate has a wall-flowconfiguration. For example, the substrate is used in a wall-flowcatalytic converter or a wall-flow particulate filter. The wall-flowconfiguration can take any one of a number of physical arrangements. Asubstrate having a wall flow configuration can have one or more theattributes described herein. Further, a substrate having a wall flowconfiguration may further comprise one or more of the following: acatalyst, a washcoat, an oxygen-storing oxide, and an emissivityenhancer Additionally, a substrate consisting of a wall flowconfiguration may be further modified, enhanced, or altered as describedherein.

In one embodiment, the channel wall thickness is any value describedbelow. Preferred channel wall thickness from about 2 mils to about 6mils. In other embodiments, the channel wall thickness ranges from about10 mils to about 17 mils. Other suitable values include 2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 mls.

In other embodiments of the wall-flow substrate, the cell density of thesubstrate is about 400 cpsi (cells per square inch) with a wallthickness of about 6 mils, or the cell density is about 900 cpsi with achannel wall thickness of about 2 mils. Additional embodiments includethose in which the cpsi is about 50, 100, 150, 200, 250, 300, or 350.

Ceramic wall-flow monoliths, which are derived from the flow-throughcellular supports used for catalytic converters, became the most commontype of diesel filter substrate. They are distinguished, among otherdiesel filter designs, by high surface area per unit volume and by highfiltration efficiencies. Monolithic diesel filters consist of many smallparallel channels, typically of square cross-section, running axiallythrough the part. Diesel filter monoliths are obtained from theflow-through monoliths by plugging channels. Adjacent channels arealternatively plugged at each end in order to force the diesel aerosolthrough the porous substrate walls which act as a mechanical filter. Toreflect this flow pattern, the substrates are referred to as thewall-flow monoliths. Wall-flow monoliths are most commonly available incylindrical shapes, although oval cross-section parts are also possiblefor space constrained applications.

Wall-flow filter walls have a distribution of fine pores which have tobe controlled in the manufacturing process. Filtration mechanism onmonolith wall-flow filters is a combination of cake and depthfiltration. Depth filtration is the dominant mechanism on a clean filteras the particulates are deposited in the inside of pores. As the sootload increases, a particulate layer develops at the inlet channel wallsand cake filtration becomes the prevailing mechanism. Certainconventional monolith filters have filtration efficiencies of about 70%of total particulate matter (TPM). Higher efficiencies can be observedfor solid PM fractions, such as elemental carbon and metal ash.

According to certain embodiments of the present invention, it ispreferred to have material which is porous so more gases can pass easilythrough the pores, interacting with catalysts deposited in the core ofthe fibrous composite. Additionally, having porous walls allows incertain embodiments for higher degree of depth filtration which wouldalso be a desirable attribute.

Substrates of the present invention in a wall flow configuration comesin much more direct contact with the exhaust gas. Material porecharacteristics (size, percent porosity, pore connectivity, open vsclosed pores, etc.) influence the physical interaction between gas andfilter material and affect such attributes as filtration efficiency andpressure drop. Furthermore, substrate durability depends on the materialresistance to chemical attack by exhaust gas components. In particular,materials need to be resistant to corrosion by metal ash which may bepart of diesel particulates. Resistance to sulfuric acid corrosion isalso required, especially if filters are used with fuels of highersulfur content. Additionally, due to the possibility of the release ofhigh quantities of heat during filter regeneration, filter materials arerequired to demonstrate excellent thermal attributes in terms ofresistance to both high temperatures and high temperature gradients.Insufficient temperature tolerance may result in melting of thematerial, while insufficient thermal shock resistance causes cracking.Other potential problems include microcracking and spallation. Inparticular embodiments, the filtering substrate and catalytic substrateof the present invention solves one or more of these problems.

Important considerations in designing the exact geometry of a wall-flowmonolith is includes the following parameters: cell density, repeatdistance (even distribution of pressure drop over the entire wall flowfilter), wall thickness, open frontal area, specific filtration area,and mechanical integrity factor.

In specific embodiments of the present invention, the wall flowconfiguration has half of the channels blocked. In anotherconfiguration, the substrate of the invention has a wall flowconfiguration wherein the blocking wall of the channel is located at thebeginning or end of a channel. In another configuration, the blockingwall is located at the middle of a channel, or alternatively is locatedanywhere between the beginning and end of a channel.

Additionally, any percentage of the channels may be included in a wallflow configuration, e.g., 10%, 25%, 50%, 75%, 90%, 95%, etc.

Channels and Channel Openings

In one embodiment, the catalytic or filtering substrate does not containa plurality of channels extending through the length of the substrate.In certain embodiments, the catalytic or filtering substrate, given itsporosity and permeability, does not need to have the channels placed inthe substrate for the substrate to function in its intended uses, e.g.,in a catalytic converter. Any potential back pressure is relieved by theporosity and permeability alone by placing the emissions in the path ofa catalytic substrate. If a membrane configuration without channels isused, a preferred use is in a low flow-rate environment so as to reducethe chance of the substrate failing structurally. The thin membraneconfiguration would preferably be used in a “low flow-rate” environmentsuch as in a fireplace or possibly a power plant. Here the flow rate islow and in some instances constant (power plant). It is understood, ofcourse, that such a configuration is suitable for use in otherapplications as well, including vehicles and stationary engines.

In another embodiment, a catalytic or filtering substrate of theinvention, in one embodiment, has a plurality of channels extendinglongitudinally through at least a portion of the substrate. Theplurality channels allow a fluid medium, e.g., a gas or a liquid, toflow through the substrate. The plurality of channels extend from thefrontal surface towards the rear surface. Other channels may extend fromthe rear surface to the frontal surface.

The channels can extend through the entire length of the substrate. Insuch an embodiment, a channel will have a first channel opening on thefrontal surface of the substrate and a second channel opening on therear surface. Alternatively, a channel extends through a portion of thesubstrate. In certain embodiments, the channel extends through about99%, 97%, 95%, 90%, 85%, 80%, 70%, 60%, or 50% of the length of thesubstrate.

The channel holes, or channel openings, of a substrate can be formed inany number of shapes. For example, the channel openings may be circular,triangular, square, hexagonal, etc. In preferred embodiments, thechannel openings are triangular, square, or hexagonal.

In one embodiment, the channel openings are formed such that thethickness of the substrate material between adjacent channels issubstantially uniform throughout the substrate. Variation in wallthickness may be from about 1% to about 50% in certain embodiments.

In another embodiment, the channels are arranged so that the walls ofadjacent channels are parallel to each other. For example, thetriangular, square, or hexagonal channels may be formed such that thewalls of adjacent channels are parallel to each other.

The diameter or cross-sectional distance of the channels in thesubstrate of the present invention can vary. In certain embodiments, thechannels have a diameter or cross-sectional distance of about 5 cm toabout 100 nm. In certain embodiments, a channel has a diameter of about100 nanometers. Other suitable values include a distance or diameterselected from about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, and 20 mils.

A channel may vary in size along its length. For example, the channelmay be about 0.04 inch across at its opening but then gradually decreasein size approaching either the end wall or point of the channel or theopening at the end of the channel. In one embodiment, the channel is asquare shape opening at the frontal surface of sides of about 10 mils.The channel extends through the length of the substrate and has a secondopening on the rear surface. The channel opening of the rear surface hasa square shape with sides of about 4 mils. The channel becomes graduallysmaller along its length from the frontal surface to the rear surface.Other similar configurations of course are contemplated.

The size of the channel opening may vary as well. For example, incertain embodiments, the diameter or (cross sectional distance) is fromabout 1 mil to about 100 mils. Other suitable ranges for the sized ofthe channel opening include, but are not necessarily limited to, about 1to about 500 mils, from about 1 to about 100 mils, from about 1 to about10 mils. Other suitable sizes include a distance or diameter selectedfrom about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,18, 19, and 20 mils. The substrate of the invention may also havechannels of varying sizes. That is, some channels of an embodiment of asubstrate has a first plurality of channels having a first diameter orcross-sectional distance and a second plurality of channels having asecond diameter or cross-sectional distance. By way of example, asubstrate of the present invention comprises, in one embodiment, one ormore channels having a cross-sectional distance of about 5 mils andfurther comprises one or more channels having a cross-sectional distanceof about 7 mils. Other variations of these embodiments are understood tobe within the scope of the present invention.

In other embodiments, the channel diameter or cross-sectional distancecan be about 5 cm, 4 cm, 3 cm, 2 cm, or 1 cm. Substrates having channelsof larger diameter or cross-sectional distance are preferred for largerexhaust systems which may have exhaust pipes of one or more feet indiameter.

The thickness of the channel wall may vary as well. For example, thechannel wall may be less than 1 mil thick. Other suitable values for thechannel wall thickness include 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 mils.

The channels can be measured in terms of the number of channels persquare inch. In certain embodiments, a substrate of the presentinvention has from about 50 to about 100,000 channels per square inch.Other suitable values include 100, 200, 300, 400, 500, 600, 700, 800,900, and 1000. Other embodiments include a catalytic or filteringsubstrate having 2000 channels per square inch.

In one embodiment, the substrate of the present invention comprises 600cpsi and a wall thickness of 6 mils. The cell density of a samplesubstrate of the present invention is compared with two samples ofcordierite. The first and second cordierite samples are 100 cpsi with 17mil wall thickness and 200 cpsi with 12 mil wall thickness,respectively. In comparison, the substrate of the present invention inthis embodiment has 600 cpsi with 6 mil walls.

In an exemplary embodiment, the substrate is drilled with 0.04 inchdiameter channels spaced every 0.06 inches across the entire filter.These channels are smaller than conventional cordierite wall flowchannels. The result is vastly increased surface area as compared tocordierite, even without taking into consideration the surface areaexisting in the massive pore space of the substrate material. Thechannels are preferably “blind” channels. Exhaust emission is forced topass through the channel walls, rather than flowing in and out of thechannels without reacting with the catalyst.

A further embodiment is directed to a catalytic or filtering substratecomprising a plurality of channels having a pyramidal shape. Thepyramidal shapes of the channels are such that they can be applied toany number of substrate materials, including and in addition to thesubstrates of the present invention, such as nSiRF-C. The pyramidalchannels can be configured such that each channel has two channelopenings, e.g., a flow through configuration having one on the frontalsurface of the substrate and one on the rear surface of the substrate.Alternatively, the pyramidal channels can be configured such that eachchannel has only one opening, e.g., a wall flow configuration. In thisembodiment, the opening of certain channels is situated on the frontalsurface, whereas the opening of other channels is situated on the rearsurface. Preferably, the channels are positioned so that adjacentchannels have the opposite configuration with respect to the location ofthe channel opening. Furthermore, in certain embodiments of thepyramidal wall flow configuration, the channel terminates at anundrilled portion of the substrate. This undrilled portion of thesubstrate may be either flat or pointed. If the undrilled portion isflat, the longitudinal cross-sectional area of the channel appearstrapezoidal. If the undrilled portion is pointed, the longitudinal crossarea of the channel appears triangular.

Shapes and Forms

The catalytic and filtering substrates comprise a number of suitable,and heretofore, unknown configurations. The substrates arethree-dimensional and generally have a front surface (or area or face)and a rear surface (or area or face) connected by the body of thesubstrate to one or more lateral surfaces. The front and rear surfacescan be any number of shapes as described herein. The front surfacerefers to the surface through which the fluid enters the substrate. Therear surface refers to the surface through which the fluid exits thesubstrate. Generally the surface is flat but may, in certainembodiments, be non-flat.

In certain embodiments, the substrate has the shape of a cylinder. Thecylinder composed of the substrate is used, for example, to catalyze thereduction of NO in a exhaust gas.

Any number of suitable lengths and widths or diameters are suitable forthe substrate of the present invention. Suitable lengths include 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20inches. Of course, longer lengths may be preferred in dieselapplications and for use in stationary engines, such as those used inpharmaceutical and chemical plants, manufacturing plants, power plants,and the like. In another respect, the shape of the substrate can bedescribed based on its frontal surface shape. The substrate of thepresent invention can be prepared such that the frontal surface has oneof several physical configurations. The frontal surface shape can be anynumber of shapes, including but not limited to circular, triangular,square, oval, trapezoidal, rectangular, and the like.Three-dimensionally, the substrates may be in the form of a cylinder ora substantially flat disc. Commercially available substrates generallyexist as one of these three designs. Substrates can have squared cornersor rounded corners. Rounded corners are preferable on the frontalsurface shape of the substrate. Thus, in one embodiment, the substrateof the present invention has a square shape with rounded corners. Inanother embodiment, the substrate has a rectangular frontal shape withrounded corners. In another embodiment, the substrate has a trapezoidalfrontal shape with rounded corners.

Exemplary dimensions for a catalytic substrate according to the presentinvention include but are not limited to, those having a circularcross-sectional shape and having a diameter of about 3.66, about 4.00,about 4.16, about 4.66, about 5.20, about 5.60, or about 6.00 inches. Inother embodiments, the catalytic substrate has the shape of a ovalcylinder with cross-sectional dimensions (minor and major axisrespectively) of about 3.15 by about 4.75 inches, about 3.54 by about5.16 inches, or about 4.00 by about 6.00 inches.

In another embodiment, the catalytic substrate has a shape and size thatis suitable for use in a head cat. Generally, a head cat will be smallerin size than conventional catalytic converters found on exhaust systemsof engines. The determination of a suitable size and shape of the headcat is within the ability of one of ordinary skill in the art. The sizeand shape of the head cat is configured based on the particular head andengine with which the head cat will be used. For example, a conventionalcordierite round substrate that is approximately 4½ inches in diameterhas a front surface area of about 28.27 square inches. On a Ford 4.6V-8, for example, there are two pre-cats having a substrate ofapproximately this dimension. These two conventional pre-cats can bereplaced by eight head-cats comprising a nSiRF-C substrate comprising adiameter of about 1.13 inches.

Alternatively, the cylinder is used to catalyze the oxidation of carbonmonoxide and unburned hydrocarbons in an exhaust gas. The length of thecylinder may be greater than, equal to, or less than the diameter of thecylinder.

Different shapes and configurations of the filtering substrate andcatalytic substrate can be used based on the particular application,e.g., stationary engine, on-road vehicle, off-road vehicle, etc.

In another embodiment, the catalytic substrate is shaped to replace thecommercially used substrate of a commercially available catalyticconverter. In this embodiment, the substrate of the invention will havea shape and dimensions that are substantially identical to substrates ofavailable catalytic converters that use a different substrate. Forexample, many catalytic converters currently used contain a substratethat is made from cordierite. The shape and size of the cordierite ofcatalytic converters is known or can be determined by analysis. Thesubstrate of the present invention is then prepared, either by machiningor molding as described below, such that the shape and size of thesubstrate of the present invention is substantially identical to that ofthe known cordierite substrate.

Membrane Configuration

Alternatively, the substrate has a membrane configuration. In such aconfiguration, the length of the substrate is substantially less thanthe width or diameter of the substrate. A longer travel length forexhaust through a substrate corresponds to a build up of backpressure incertain conventional catalytic converters and particulate filters. Inthe thinner substrate of certain embodiments of the present invention,backpressure will be minimized, and the exhaust gas will move throughthe filter system with less effort and increased filtering capabilities.This reduction in backpressure results in the engine running moreefficiently meaning better gas mileage and more power.

In one embodiment of the present invention, the substrate is two inchesin diameter and 1/16th inches thick and has 400 times the surface areaof a conventional cordierite filter that has a four inch diameter and issix inches long. Since the substrate itself has been reduced in size, acanister can also be reduced in size, resulting in just a small bulge inthe exhaust line. Alternatively, the substrate can be housed in theexhaust manifold.

In another embodiment, the substrate is in the form of a membrane. Inthis instance, the membrane comprising the substrate material asdescribed herein having any number of shapes as described above, andwherein the length of the substrate is substantially less than the widthor diameter. The dimension can be described as a ratio of, e.g., widthto length, or diameter to length. Suitable diameter to width ratiosinclude, but are not limited to, about 20:1, 19:1, 18:1, 17:1, 16:1,15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, and 5:1.

Furthermore, a substrate having a membrane configuration can be stackedtogether with one or more separate substrate embodiments. With amembrane configuration, a number of catalytic or filtering substrateshaving a membrane configuration can be stacked together. For example, aplurality, e.g., 5, of catalytic or filtering substrates having acylinder (or disc) shape with a diameter of about 1 inch and a length ofabout 0.2 inch can be stacked together to form a substrate pile having acertain length, e.g., about 1 inch.

In the case of a membrane configuration, in one embodiment, thecatalytic substrate does not contain a plurality of channels runningthrough the substrate. Because of the shorter distance through which thegas must travel and because, in part, of the high porosity of and lowdrop pressure caused by the present invention, it is possible to form asubstrate pile comprising a plurality of catalytic substrates having amembrane configuration.

Furthermore a stacked membrane configuration also includes stackedmembrane configurations in which the individual substrates are notperpendicular to the floor of the catalytic converter or particulatefilter. In this embodiment, the substrate may be machined or molded sothat the angle between the side(s) (lateral surface) of the substrateand the face (front or rear surface) is about 90° or is less than orgreater than 90°, e.g., 80°, 70°, etc.

Pre-Sintering Addition of Catalyst

In another embodiment, the catalytic substrate as described hereinfurther comprises a catalyst, wherein the catalyst is added to thesubstrate material prior to the sintering process. In this case, thecatalyst is generally added to the slurry before the green billet isproduced. In other embodiments, the catalyst is added to the fibers inthe mixer. Alternatively, the catalyst, if in the form of a liquid, isadded to the slurry in certain embodiments. The substrate may be formedfrom a slurry that comprises one or more catalysts. In one embodiment,the catalyst, upon sintering, adheres to the fibers of the substrate. Inanother embodiment, the catalyst is located within the pores of channelwalls as opposed to be adhered mainly to the surface of the channelwalls.

Zonation of Substrate

In another embodiment, the catalytic substrate as described herein isprepared such that different zones in the substrate have differentattributes. In other words, one or more physical characteristics orattributes of the catalytic substrate are not uniform, or the same,throughout the entirety of the substrate. For example, in certainembodiments, different zones or regions of the substrate have differentdensities, different catalysts, different catalyst mixtures, differentchannel configurations, different porosities, different permeabilites,and/or different thermal attributes. By way of example, in oneembodiment, a catalytic substrate of the present invention comprises anSiRF-C composite and a first and second catalyst, wherein said firstcatalyst is applied to a first zone of said substrate and said secondcatalyst is applied to a second zone of said substrate. In a furtherembodiment, the substrate has a different degrees of structuralintegrity through the body of the substrate. For example, as describedherein, a densification coating may be added to the surface of thesubstrate to increase hardness of its surface which would lessenpossible damage.

Washcoat

Another aspect of the present invention is directed to a catalytic orfiltering substrate as described herein further comprising a washcoat.In other embodiments, the catalytic substrate further comprises acatalytic washcoat, e.g., the washcoat comprises a catalyst in additionto a washcoat material. Alternatively, in another embodiment, thewashcoat material has catalytic activity.

Suitable washcoats include silica, titania, unimpregnated zirconia,zirconia impregnated with a rare earth metal oxide, ceria, co-formedrare earth metal oxide-zirconia, and combinations thereof. Othersuitable washcoats are disclosed in, e.g., U.S. Pat. Nos. 6,682,706;6,667,012; 4,529,718; 4,722,920; 5,795,456; and 5,856,263, all of whichare herein incorporated by reference in their entirety.

Generally, a washcoat can be applied in certain embodiments, from anaqueous slurry. The alumina powder and/or other washcoat oxides aremilled to the required particle size. The particle size distribution ofthe washcoat powder affects the mechanical strength of the finishedwashcoat and its adhesion to the substrate, as well as the rheologicalattributes of the slurry during the washcoating process. Alumina, a veryhard material, is, in certain embodiments, milled using air-jet or ballmills.

In the next step, the materials are dispersed in acidified water in atank with a high-shear mixer. The solid content in the slurry istypically 30-50%. After prolonged mixing, the alumina suspension becomesa stable colloidal system.

The amount of washcoat deposited on the substrates depends on, and canbe controlled by, the rheological attributes (viscosity) of the slurry.The aluminum oxide slurry, in certain instances, is a nonnewtonian fluidwhich changes its viscosity with time and with the amount of mechanicalenergy supplied to the system (shear rate). At any steady sheer rate,the viscosity of the slurry is a function of its pH. In certainembodiments, the viscosity can be controlled by pH adjustment. Preciseviscosity control, however, is probably the biggest challenge in thewashcoating process due to the nonnewtonian character of aluminasystems.

The washcoat slurry can be applied to the substrates using any knownmethods and procedures, including dipping or pouring over the parts,and/or in a specialized coating machine. Excess slurry is cleared fromchannels with compressed air. The substrates can then be dried andcalcined to bond the washcoat to the monolith walls.

In certain embodiments, the washcoat can be applied in one, two, or morelayers. Each layer can be dried and calcined before the processing ofnext layer. There are several reasons for the application of multi-layerwashcoats: (1) the catalyst design may require a different chemicalformulation for each layer, and (2) coating/process equipmentconstraints, e.g., an inability to handle very viscous slurries whichare needed to apply a thick washcoat in one-pass operation.

Typical thickness of the washcoat layer is 20-40 μm but values outsideof the range can also be used in the present invention. These numberscorrespond, for example, to a washcoat loading of about 100 g/L on a 200cpsi substrate, up to about 200 g/L on a 400 cpsi substrate. Thespecific surface area of catalyst washcoat materials is in certainembodiments between 100 and 200 m²/g. Of course, other values are usefulin the present invention.

Noble metals and other catalysts in a complex catalyst system may reactwith each other, with washcoat components, or with the support materialand produce undesired, catalytically inactive compounds. If suchreactions occur in a given catalytic system, they are difficult toprevent in the conventional washcoat technology. Since the catalyticmetals are impregnated onto the finished washcoat layer, the contactbetween reacting components cannot be avoided.

Segregated washcoat technologies have been developed to physicallyseparate noble metals by fixing them on a particular base metal oxide ofthe washcoat before the washcoat is applied to the substrate. Throughthe use of washcoat layers with different oxides and/or noble metals,the components of a catalytic system can be separated. Additionalbenefit of this technology include a control of the noble metal/basemetal ratio and an improved noble metal dispersion. Such technology canbe applied to the present invention. Thus, in a preferred embodiment,the present invention is directed to a catalytic substrate comprising anSiRF-C, at least two catalytic metals, and a washcoat, wherein said twocatalytic metals are physically separated.

Segregated Washcoat Schematic: Segregated washcoats were first appliedfor automotive 3-way catalysts. An example of such a catalyst is atri-metal system which includes platinum, palladium and rhodium. Thefirst layer of the catalyst is composed of Pd/Al₂O₃. The second(surface) layer is composed of Rh/Pt/Ce—Zr. That design prevents theformation of palladium-rhodium alloys which otherwise could causecatalyst deactivation.

Aluminum oxide or alumina is the basic material for emission controlcatalyst washcoat. The high surface area gamma crystalline structure(γ-Al₂O₃) is used for catalyst applications. It is characterized by highpurity. Presence of certain elements in the Al₂O₃ can influence itsthermal stability, both negative and positive. Small amounts of Na₂Opresent in Al₂O₃ act as a flux, enhancing the sintering of alumina. Incontrast, several metal oxides, including La₂O₃, SiO₂, BaO, and CeO₂have a stabilizing effect on alumina surface area and reduce itssintering rate. Stabilized aluminas are commercially available.

In other embodiments, cerium dioxide, or ceria, is a component of thecatalyst washcoat, added, for example, in quantities of up to 25%. Inother embodiments, ceria is add in quantities of about 5%, 10%, 15%,20%, and 25%. Ceria is an important promoter in the automotive emissioncontrol catalyst. One function of ceria in the three-way catalyst isoxygen storage, which is possible through a cycling between Ce⁴⁺ andCe³⁺. Other effects attributed to ceria include stabilization ofalumina, promotion of the steam reforming reaction, promotion of noblemetal dispersion, and promotion of noble metal reduction.

Certain diesel oxidation catalyst formulations include high loadings ofceria. The function of ceria is catalytic oxidation/cracking of thesoluble organic fractions of diesel particulates.

High surface area cerium oxide can be produced, for example, bycalcination of cerium compounds. The BET surface area of ceria can be ashigh as 270 m²/g. In other embodiments, for example in a three-waycatalyst, ceria of about 150 m²/g surface area is used. High temperaturestabilized varieties, which are capable of withstanding 900-1000° C.,have surface areas of about 6-60 m²/g and are suitable for use in thepresent invention.

A catalytic substrate or filtering substrate of the invention in otherembodiments further comprises zirconium oxide. In certain embodiments,the zirconium oxide increases the thermal stability of the substrate.

Titanium dioxide is used with some diesel catalysts as an inert,non-sulfating carrier. Two important crystal structures of titaniumdioxide include anatase and rutile. The anatase form is important forcatalyst applications. It has the highest surface area of 50-120 m²/gand is thermally stable up to 500° C. The rutile structure has a lowsurface area of below 10 m²/g. A conversion of anatase into rutile,which takes place at about 550° C., leads to catalyst deactivation. Inanother embodiment of the present invention, the catalytic substratecomprises a nSiRF-C, preferably an AETB or OCTB, a catalyst, andtitanium oxide.

Zirconium oxide can be used as a thermal stabilizer and promoter ofceria in the automotive three-way catalyst and also as a non-sulfatingcomponent of diesel oxidation catalyst washcoats. Zirconium oxide has aBET surface area of 100-150 m²/g. It rapidly looses its surface area at500-700° C. Better thermal stability can be achieved by the use of awide range of dopants including La, Si, Ce, and Y.

Zeolites are synthetic or naturally occurring alumina-silicate compoundswith well defined crystalline structures and pore sizes. The dimensionsof zeolite pores are typically between 3 and 8 Å, which falls into therange of molecular sizes. Any molecule of a larger cross-sectional areais prevented from entering the channel of the zeolite cage. For thisreason, zeolites are often referred to as molecular sieves. Zeolites arecharacterized by high specific surface areas. For example, the ZSM-5zeolite has surface area of about 400 m²/g. Zeolite mordenite has asurface area of about 400-500 m²/g. Most zeolites are thermally stableup to 500° C.

Zeolites for some catalytic applications are ion exchanged with metalcations. The acid form of zeolite (HZ) is first treated with an aqueoussolution containing NH⁴⁺ (NH₄NO₃) to form the ammonium exchanged zeolite(NH⁴⁺Z⁻). This is then treated with a salt solution containing acatalytic cation forming the metal exchanged zeolite (MZ).

Zeolites, due to their repeatable and well defined pore structure, areexcellent adsorption materials. They have been used as adsorbents innumerous applications including drying, purification and separation.Synthetic zeolites are also used as catalysts in petrochemicalprocessing.

In recent years, zeolites have been increasingly used for dieselemission control, both as catalysts (SCR, lean NO_(x) catalyst) andadsorbers (hydrocarbon traps in diesel oxidation catalysts).

It is understood that further embodiments of the invention include anyof the specific substrate embodiments described herein, furthercomprising any of the specific washcoat embodiments.

Oxygen-Storing Oxide

In another embodiment, the catalytic substrate or filtering substrate ofthe present invention further comprises an oxygen-storing oxide. Theoxygen-storing oxide, for example CeO₂, has an oxygen storing capacity(hereafter abbreviated as “OSC”), that is, the capacity to occludegaseous oxygen and to release the occluded oxygen. More specifically,CeO₂ is added for adjusting the oxygen concentration of gaseousatmosphere, so that excess oxygen in the gaseous atmosphere is occludedinto the crystalline structure of CeO₂ in an oxygen-rich state (i.e.,fuel-lean state which may be simply referred to as “lean state”) forassisting the catalytic converter in reducing NO_(x) to N₂ whilereleasing the occluded oxygen into the gaseous atmosphere in a CO-and/or HC-rich state (i.e., fuel-rich state which may be simply referredto as “rich state”) for assisting the catalytic converter in oxidizingCO and HC to CO₂ and H₂O. Thus, the catalytic activity of the catalyticsubstrate is enhanced by the addition of CeO₂. Other oxygen-storingoxides include Pr₆O₁₁ and the like, as disclosed in U.S. Pat. No.6,576,200. Further embodiments include any specific substrate embodimentdescribed herein, further comprising an oxygen-storing oxide, e.g.,CeO₂.

SOx Oxidation

In the presence of certain metal catalysts, especially platinum, sulfurpresent in the fuel, for example in diesel fuel, is converted to SOxwhich can then create environmentally harmful sulfuric compounds, suchas sulfuric acid fumes, in the exhaust. Most sulfates are typicallyformed over platinum catalysts at relatively high exhaust temperaturesof about 350-450° C. While there is a dire need to remove sulfur fromthe gasoline and diesel fuel formulations, in the interim, catalystformulations have tried to reduce that problem to their best possibleextent.

An exemplary platinum catalyst developed by Engelhard is composed of5-150 g/ft³ Pt/Rh at 5:1 ratio and 30-1500 g/ft³ of MgO (U.S. Pat. No.5,100,632 (Engelhard Corporation)). The catalyst can be impregnated ontosubstrates from water based solutions. A filter coated with the catalystpreferably is used for exhaust temperatures of 375-400° C. toregenerate. The function of rhodium in the above formulation is tosuppress the catalytic oxidation of SO₂ and, thus, the sulfate mask inthe catalyst.

A catalytic substrate of the present invention may, in certainembodiments, provide solutions to these problems by, for example, havingan improved thermal profile and thereby reducing thermal breakdown ofthe catalyst.

Catalyst poisoning is a significant source of catalyst deactivation. Itcan occur when substances which are present in exhaust gases chemicallydeactivate the catalytic sites or cause fouling of the catalyticsurface. Poisons in exhaust gases from internal combustion engines maybe derived from lube oil components or from the fuels.

Interactions between different catalyst species or between catalystspecies and carrier components are another temperature-induced mode ofcatalyst deactivation. An example is the reaction between rhodium andCeO₂ in an automotive three-way catalyst. This type of problem can bereduced by using alternative carriers and special washcoat technologieswhich physically separate the reacting components and are known in theart.

A further advantage of the present invention is that a nSiRF-C can bepumped with different zones to separate physically incompatiblecomponents, or alternatively can be utilized as a stacked membraneconfiguration with incompatible components in separate membranesubstrates.

Catalyst deactivation may also occur due to a physical washcoat lossthrough erosion and attrition. That mechanism may also be important foremission control catalyst because of the high gas velocities,temperature changes, and differences in thermal expansion between thewashcoat and substrate materials.

Catalyst Cover

In certain applications, adsorber catalysts are used to convert NO_(x)into salts which can then be manually removed in a regenerative process.However, the presence of sulfur in the fuel can lead to the formation ofinsoluble SO₄ salts, such as barium sulfate, which can form a protectivecoating on top of the catalysts and reduce their efficiency. Anadvantage of certain embodiments of the present invention is that thecatalytic substrate is less susceptible to reduced efficiency due to thecoating from sulfate salts.

In another embodiment, the catalytic substrate or filtering substrate ofthe present invention further comprises a protective coating suitablefor ceramics. For example, such a suitable protective coating isdisclosed in U.S. Pat. No. 5,296,288, which is incorporated herein byreference in its entirety. This coating is also known as ProtectiveCoating for Ceramic Materials (PCC). Another suitable, and relatedcoating, is available as Emisshield™ coating (Wessex Incorporated,Blacksburg, Va.). The emissivity agents in Emisshield™ enhance theemissivity of materials, especially at high temperatures. Additionally,a protective coating may lessen damage from external impact and wearforces. Suitable coatings are disclosed in U.S. Pat. Nos. 5,702,761 and5,928,775, issued to DiChiara, Jr. et al. and U.S. Pat. No. 5,079,082,issued to Leiser, et al., the disclosures of which are incorporatedherein by reference. Said coating can be used with one or more of thespecific filtering and catalytic substrates described herein.

In certain embodiments, the catalytic substrate or filtering substrateis resistant to damage from thermal shock and thermal cycling. However,certain substrates are relatively soft and can be damaged by externalimpact and wear forces. To lessen such damage, in a preferredembodiment, the catalytic or filtering substrate of the presentinvention further comprises one or more protective coatings to thesurface, preferably the exterior surface, of the substrate. Examples ofsuitable protective coatings are disclosed in U.S. Pat. Nos. 5,702,761and 5,928,775, and 5,079,082, the disclosures of which are incorporatedherein by reference. Thus, in a preferred embodiment, the inventionprovides a substrate having, among other attributes, a higher porosity,a higher permeability, and a sufficient hardness compared toconventional substrates. Said coating can be used with one or more ofthe specific filtering and catalytic substrates described herein.

Pressure Drop

The present invention also provides a substrate that provides for animproved pressure drop for catalytic converters and particulate filters.Thus, in certain embodiments, a substrate of the present inventionpermits one to provide a means for removing and/or filtering an exhaustgas without a substantial buildup of back pressure, or alternativelywith a lower buildup of back pressure compared to conventional catalyticand particulate filters.

The flow of exhaust gas through a conventional catalytic convertercreates a substantial amount of backpressure. The backpressure buildupin a catalytic converter is an important attribute to catalyticconverter success. If the catalytic converter is partially or whollyclogged, it will create a restriction in the exhaust system. Thesubsequent buildup of backpressure will cause a drastic drop in engineperformance (e.g., horsepower and torque) and fuel economy, and may evencause the engine to stall after it starts if the blockage is severe.Conventional attempts to reduce pollutant emissions are very expensive,due to both the cost of materials and retrofitting or manufacturing anoriginal engine with the appropriate filter.

A substrate of the present invention has, in certain embodiments, theattribute of producing a lower or smaller pressure drop thanconventional substrates used in catalytic converters or particulatefilters. The present invention in some embodiments provides a lowerbuildup of soot in the particulate filter and in some instances allowsless frequent need for replacement of the filter compared toconventional particulate filters.

Specific Embodiments

The present invention is also directed to specific embodiments of thecatalytic and filtering substrates described above. Specific embodimentsinclude a substrate comprising, or alternatively consisting of orconsisting essentially of, a nSiRF-C and a catalyst. An additionalembodiment is a filtering substrate comprising a nSiRF-C and a pluralityof channels.

For example, certain embodiments of the substrate have a plurality ofthe attributes described above. In other embodiments, the substrate ofthe invention has 2, 3, 4, 5, 6, 7, 8, 9, or 10 of the attributesdescribed above. The specific embodiments can comprise any combinationof attributes. The catalytic substrate is further illustrated by thefollowing nonlimiting specific embodiments.

In one embodiment, the substrate of the invention comprises a nSiRF-Ccomposite having a porosity of about 96% to about 99%; a density ofabout 10 to about 14 lb/ft³; a plurality of channels having a wall-flowconfiguration; and optionally a catalyst.

In one embodiment, the substrate of the invention comprises a nSiRF-Ccomposite comprising aluminaboriasilica fibers, silica fibers, andalumina fibers having a porosity of about 96% to about 99%; a density ofabout 10 to about 16 lb/ft³, preferably about 10, 11, 12, 13, 14, 15, or16 lb/ft³; a plurality of channels having a wall-flow configuration; andoptionally a catalyst. In other embodiments, the substrate furthercomprises a washcoat, preferably of aluminaoxide or a derivated thereof.

In another embodiment, the substrate of the invention comprises asubstrate having one or more of the following attributes: tensilestrength of from about 100 to about 150, preferably about 130 to about140, more preferably about 133 psi; thermal conductivity of about 0.5 toabout 0.9, preferably about 0.7 to about 0.8, more preferably about0.770 BTU-ft*/hr ft²° F.; a thermal coefficient of expansion of about 1to about 5×10⁻⁶, from about 1 to about 3×10⁻⁶, more preferably about1.95×10⁻⁶ (tested from 77° F.-1000° F.); an average density of fromabout 15.5 to about 17, preferably about 16 to about 16.8, morepreferably about 16.30/lb/ft³; and optionally a catalyst.

In another embodiment, the substrate of the invention comprises asubstrate having one or more of the following attributes: tensilestrength of about 50 to about 70, preferably about 60 to about 65, morepreferably about 63 psi; thermal conductivity of about 0.5 to about 0.9,preferably about 0.7 to about 0.8, more preferably about 0.770BTU-ft*/hr ft² ° F.; a thermal coefficient of expansion of about 1 toabout 5×10⁻⁶, from about 1 to about 3×10⁻⁶, more preferably about1.77×10⁻⁶ (tested from 77° F.-1000° F.); an average density of fromabout 7 to about 9, preferably about 8.2 to about 8.6, more preferablyabout 8.40/lb/ft³; and optionally a catalyst.

In another embodiment, the substrate of the invention comprises asubstrate having one or more of the following attributes: tensilestrength of about 60 to about 80, preferably about 70 to about 79, morepreferably about 74 psi; thermal conductivity of about 0.5 to about 0.9,preferably about 0.7 to about 0.8, more preferably about 0.765BTU-ft*/hr ft² ° F.; a thermal coefficient of expansion of about 1 toabout 5×10⁻⁶, from about 1 to about 3×10⁻⁶, more preferably about1.84×10⁻⁶ (tested from 77° F.-1000° F.); an average density of fromabout 9 to about 11, preferably about 9.5 to about 10.5, more preferablyabout 10 lb/ft³; and optionally a catalyst.

Another suitable catalytic substrate of the present invention is anSiRF-C as described herein; and a catalyst comprising: a carrierpre-doped with copper oxide (CuO); at least one precious metal as a maincatalyst selected from the group consisting of platinum (Pt), palladium(Pd), rhodium (Rh) and rhenium (Re), wherein the at least one preciousmetal is doped on the surface of the pre-doped carrier; and at least onemetal oxide as a co-catalyst selected from the group consisting ofantimony trioxide (Sb₂O₃), bismuth trioxide (Bi₂O₃), tin dioxide (SnO₂),and mixtures thereof, wherein the at least one metal oxide is doped onthe surface of the pre-doped carrier. Such a catalyst is described inU.S. Pat. No. 6,685,899, which is incorporated by reference in itsentirety.

In one embodiment, the substrate is suitable for being used in acatalytic converter that is placed inside the engine head before theexhaust manifold in relation to the flow of exhaust gas.

Additional embodiments of the catalytic substrate include a catalyticsubstrate comprising an nSiRF-C composite having the approximateattributes shown in the following table.

Embodiment 1 Embodiment 2 Embodiment 3 Thermal 4-100 × 10⁻² W/m-K 5-7 ×10⁻² W/m-K 6.04 F-02 W/m-K Conductivity Specific Heat 10-150 J/mol K600-700 × 10⁻² J/kg-K 640 × 10⁻² J/kg-K Density .05-5 gm/cc 0.1-0.3gm/cc 0.2465 gm/cc Emissivity .68-.97 0.7-0.92 0.88 Axial Strength 1.5to 3.5 MPa 2-3 MPa 2.21 MPa Noise Attenuation 40-100 db 70-80 db 74 dbat 3500 rpm Porosity 80-99% 97-98% 97.26% Permeability At least 600900-∞ cd 1093-∞ cd Regeneration Time 0.5 to 1.5 sec 0.6-0.9 0.75 secSurface Area 70,000-95,000 in² 88,622 in² Melting Point 1700-50003000-4000° C. 3,000° C. Thermal Expansion 0.001 × 10⁻⁶ to 9 × 10⁻⁶ 0.1 ×10⁻⁷ to 0.4 × 10⁻⁷ 0.25 × 10⁻⁷ 1/C. (CTE)

Another specific embodiment is directed to a catalytic substratecomprising an nSiRF-C as described in Table 1; and a catalyst selectedfrom the group consisting of palladium, platinum, rhodium, derivativesthereof, and combinations thereof.

A preferred substrate comprising high-grade non-woven refractory fibersis 90% to 98% porous and has an emissivity value between 0.8 and 1.0.

In one embodiment, the filtering substrate of the present inventioncomprises or consists essentially of a nSiRF-C and further includes afrontal inlet end and an outlet end, a matrix of thin, porous,intersecting vertically extending walls and horizontally extendingwalls, which define a plurality of channels extending in a substantiallylongitudinal and mutually parallel fashion between the frontal inlet endand the outlet end; the frontal inlet end includes a first section ofcells plugged along a portion of their lengths in a non-checkeredpattern and a second section of cells plugged in checkered pattern, thefirst section of non-checkered plugged cells being smaller than thesecond section of checkered plugged cells. Such a configuration isfurther described in U.S. Pat. No. 6,673,414, which is hereinincorporated by reference in its entirety. Up to three-fourth of thecells of the first section may be unplugged. Alternatively, up toone-half of the cells of the first section may be unplugged.Alternatively, up to one-fourth of the cells of the first section may beunplugged.

It is further understood that the invention is directed to embodimentsconsisting of or consisting essentially of the limitations of thevarious embodiments. Thus, for example, having described one embodimentas a catalytic substrate comprising a nSiRF-C and a catalyst, it isunderstood that the invention further encompasses a catalytic substrateconsisting of or consisting essentially of a nSiRF-C and a catalyst.

Methods of Catalyzing a Reaction and Filtering

Another aspect of the invention is directed to a method of catalyzing areaction comprising providing a catalytic substrate of the presentinvention; and directing a flow of a fluid over and/or through thecatalytic substrate at a temperature sufficient to catalyze saidreaction. Preferably, the reaction converts pollutants tonon-pollutants. For example, the catalytic substrate in one embodimentconverts carbon monoxide to carbon dioxide.

The method of catalyzing is performed using a substrate comprisingalumina enhanced thermal barrier as described herein. A number ofsubstrates

In a preferred embodiment, the substrate contains a suitable catalysis.

In one embodiment, the present invention is directed to a method offiltering an exhaust gas comprising providing a filtering or catalyticsubstrate of the present invention as described above, and directing aflow of a fluid, e.g., a gas or liquid, through the substrate, whereinsaid gas contains particulate matter.

In another embodiment, the method further comprises burning off of thefiltered particulate matter. The burning off of the filtered particulatematter converts the accumulated particulate matter mainly intononpollutant matter, such as, for example, gaseous compounds.

This aspect of the present invention is of particular use with dieselengines. In another aspect, the invention is directed to a method offiltering wherein the filtering utilizes a diesel particulate filter.

Diesel engines (where compression alone ignites the fuel) have recentlycome under worldwide scrutiny for their exhaust emissions, which containa large number of harmful particulates in addition to toxic gases.Manufacturers' response has been to apply known catalytic convertertechnology to diesel engines. Unfortunately, regulations regardingemission standards have exceeded the physical and economic limitationsof conventional catalytic converters. Diesel emissions differ fromgasoline emissions in that a greater amount of particulate matter isgenerated. For this reason, existing technology for exhaust emissioncapture, combustion, and oxidation will not comply sufficiently with themost stringent emission standards.

A majority of buses are manufactured with or are retrofitted with 85%efficient diesel particulate traps [“DPTs”]. DPTs have a high cost, arehighly complex, lower fuel economy, and have low durability. Furtherregulations require 100 percent compliance by 2010 and DPTs alone cannotsatisfy these regulatory requirements. The high temperature of an engineor exhaust gas permits the particulate matter to combust with a shorterresidence time. Moving the filter closer to the combustion chamber ofthe engine or adding an auxiliary heat source can provide increasedheat. Therefore, what is needed is a filter that (1) can be placed inextremely high temperatures, i.e., above 500 degrees Celsius, such asnear the combustion chamber; (2) is more resistant to vibrationdegradation; and (3) still maintains or improves particulate matterburning effect. The ability to achieve particulate matter burning evenwithout a catalyst would also provide significant savings on catalystand coating costs.

Once a filter captures particulate matter (e.g., soot), the particulatematter needs to be completely combusted by raising its temperaturesufficiently in the presence of oxygen. Combustion of the particulatematter can be accomplished by utilizing the existing temperature of theexiting exhaust and/or providing an auxiliary source of heat. The timeit takes to burn the particulate matter at this temperature is referredto as the required “residence time,” “regeneration time,” or “burnoff”period. A shorter residence time of particulates in the substrate porestranslates into a reduced occurrence of pore-clogging build up, whichbuildup can cause increased gas flow backpressure requiring excessiveenergy to operate efficiently. Lower residence time is, therefore,preferred.

One conventional DPT is exemplified in U.S. Pat. No. 5,611,832 (IsuzuCeramics Research Institute Co., Ltd.), which discloses a DPT forcollecting particulates from exhaust gas discharged from a dieselengine. The DPT filter is constituted of a woven inorganic fiber coveredwith a silicon carbide ceramic, and metallic wire nets disposed therebetween.

Additional uses of a filtering substrate or catalytic substrate includesability to clean or filter from a fluid flow such pollutants andimpurities as: dust/soot, smoke, pollen, fluids, bacteria/viruses, odor,oil, volatile organic compounds, liquids, methane, ethylene, and a widevariety of other chemicals, including those chemicals listed as theEPA's 188 “toxic air pollutants.”

A method of catalyzing a reaction and/or filtering a fluid may be usefulin any number of industries or applications, in particular one or moreof the following: Aerospace Industry; Asbestos; Asphalt Roofing andProcessing; Auto and Light Duty Truck (surface coating); Benzene WasteOperations; Boat Manufacturing; Brick and Structural applications; ClayProducts Manufacturing; Cellulose Products Manufacturing;Caroxymethylcellulose Production; Cellulose Ethers Production; CelluloseFood Casing Manufacturing; Cellophane Production; ChromiumElectroplating; Coke Oven: Pushing, Quenching, & Battery Stacks; CokeOvens; Combustion Turbines; Degreasing Organic Cleaners; Dry Cleaning;Engine Test Cells/Stands; Fabric Printing, Coating& Dyeing; FerroalloysProduction; Flexible Polyurethane Foam; Fabrication Operation; FlexiblePolyurethane Foam Production; Friction Products Manufacturing; GasolineDistribution (Stage 1); General Provisions; Generic MACT; HazardousWaste Combustion; Hazardous Organic NESHAP; Hydrochloric AcidProduction; Industrial, Commercial and Institutional Boilers; IndustrialCooling Towers Process Heaters; Integrated Iron & Steel; Iron Foundries(surface coating); Leather Finishing Ops.; Lime Manufacturing; MagneticTape; Manufacturing Nutritional Yeast; Marine Vessel Loading Operations;Mercury Cell Chlor-Alkali Plants; Metal Coil (surface coating); MetalCan (surface coating); Metal Furniture (Surface Coating); Mineral WoolProducts; Misc. Coating Manufacturing; Misc. Metal Parts and Products;Municipal Solid Waste Landfills; Natural Gas Transmission and Storage;Off-Site Waste Recovery Operations; Oil & Natural Gas Production;Organic Liquids Distribution (non-gasoline); Paper & Other Web (SurfaceCoating); Pesticide Active Ingredient Production; Petroleum Refineries;Pharmaceuticals Production; Phosphoric Acid/Phosphate Fertilizer;Plastic Parts (Surface Coating); Polymers and Resins; Polyether PolyolsProducts; Polybutadiene Rubber; Polysulfide Rubber; Phenolic Resins;Polyethylene Terephthalate; Polyvinyl Chloride and CopolymersProduction; Portland Cement Manufacturing; Primary Aluminum Production;Primary Lead Smelting; Primary Copper; Primary Magnesium Refining;Printing/Publishing; Publicly Owned Treatment Works (POTW); Pulp & Paper(non-combust) MACT I; Pulp & Paper (non-chem) MACT III; Pulp and Paper(combustion sources) MACT II; Pulp & Paper Mills; Reciprocating Int.Combust. Engine; Refractory Products Manufacturing; Reinforced PlasticComposites Production; Secondary Aluminium; Secondary Lead Smelters;Semiconductor Manufacturing; Shipbuilding & Ship Repair; SiteRemediation; Solvent Extraction for Vegetable Oil Production; SteelPickling-HCL Process; Taconite Iron Ore Processing;Tetrahydrobenzaldehyde Manufacturing; Tire Manufacturing; Wet FormedFiberglass; Mat Production; Wood Building Products; Wood Furniture; andWool Fiberglass Manufacturing. Such industries and applications oftenutilize EPA-regulated stationary sources of emissions.

Other suitable uses include a filtering or catalytic process in one ormore of the following applications: Cars (dust/soot, odor, oilfiltration, VOC, methane, other chemicals (gaseous, solid, or liquid));Water Jets (dust/soot, odor, oil filtration, VOC, methane, otherchemicals (gaseous, solid, or liquid)); Snowmobiles (dust/soot, odor,oil filtration, VOC, methane, other chemicals (gaseous, solid, orliquid)); Small engine (dust/soot, odor, oil filtration, VOC, methane,other chemicals (gaseous, solid, or liquid)); Motorcycles (dust/soot,odor, oil filtration, VOC, methane, other chemicals (gaseous, solid, orliquid)); Mobile Diesel Engines (dust/soot, odor, VOC, methane, otherchemicals (gaseous, solid, or liquid)); Stationary Diesel Engines(dust/soot, odor, VOC, methane, other chemicals (gaseous, solid, orliquid)); Power Stations (dust/soot, odor, VOC, methane, other chemicals(gaseous, solid, or liquid)); Refineries (VOC, other chemicals (gaseous,solid, or liquid)); and Chemical and Pharmaceutical Manufacturing(dust/soot, bacteria/virus, odor, oil filtration, VOC, methane, otherchemicals (gaseous, solid, or liquid).

Furthermore, additional catalytic and/or filtering applications includethe use of a substrate according to the present invention in one or moreof the following areas: Agricultural & Forestry Incineration Emissions;Bakeries (dust/soot, smoke, odor, VOC, other chemicals (gaseous, solid,or liquid)); Bio-Medical Fluid Filtration; Breweries and wineries(odor); Cabin air (car, submarine, space industry, airplane) (dust/soot,smoke, pollen, bacteria/viruses, odor, VOC, other chemicals (gaseous,solid, or liquid)); Clean room applications (dust/soot, smoke, pollen,bacteria/viruses, odor, oil, VOC, methane, other chemicals)); CommercialIncineration Emissions (odor, VOC, other chemicals (gaseous, solid, orliquid)); Commercial Toxic Organic Emissions; Dry cleaners (VOC, otherchemicals (gaseous, solid, or liquid)); Evaporative Emissions (such asFuel Evaporation Management); Fireplaces); Flame grilling (fast food)(dust/soot, smoke, odor, VOC, other chemicals (gaseous, solid, orliquid); Fitness Centers); Fluid Filtration in General (Drinking watertreatment)); Food processing and storage (odor, other chemicals(gaseous, solid, or liquid); Foundries (odor); Fuel Cells (VOC, methane,other chemicals (gaseous, solid, or liquid); Gas Masks (dust/soot,smoke, pollen, bacteria/viruses, odor, VOC, other chemicals (gaseous,solid, or liquid); General VOC applications for processing/manufacturing(wood products, coating industry, textile industry, etc);Glass/ceramics; Greenhouses; Home appliances—cold (Rechargeableappliances) (odor, oil, VOC, other chemicals (gaseous, solid, orliquid)); Home appliances—hot (Water Heaters & Domestic HeatersAppliances) (odor, oil, VOC, other chemicals (gaseous, solid, orliquid)); HVAC Sanitation); Hydrogen Reformation (VOC, methane, otherchemicals (gaseous, solid, or liquid)); Medical Growth Medium; Officebuildings; Oil/petrol transport; Other Electro-Magnetic Insulation(Electro-Magnetic Shield); Paint usage; Petrol stations (odor, VOC);Polymer processing (odor, VOC, other chemicals (gaseous, solid, orliquid); Recovery of precious metals/catalysts from hot gases andliquids; Restaurant Fumes; Sewage and bio-waste (bacteria/viruses, odor,VOC, methane, other chemicals (gaseous, solid, or liquid)); Slaughterhouses; Smoke Houses (dust/soot, smoke); Sound Insulation; Swimmingpools; Tanning studios; Tunnels and car parks (dust/soot, odor, VOC,methane, other chemicals (gaseous, solid, or liquid)); and WasteIncineration (dust/soot, odor, VOC, other chemicals (gaseous, solid, orliquid)).

Process of Preparing a Catalytic or Filtering Substrate

In another aspect, the present invention is directed to a process ofpreparing any one of the substrates (catalytic or filtering) asdescribed herein. The present invention is also directed to a process ofpreparing a catalytic substrate of the present invention. In anotheraspect, the present invention is directed to process of preparing adiesel particulate filter. A number of methods as described below can beused to prepare the substrate.

In one aspect of the present invention, a catalytic substrate asdescribed herein can be prepared using a commercially available billetof nSiRF-C. The commercially available billet of nSiRF-C is machinedinto a suitable shape, form, and size. A substrate of the invention canbe prepared by as large brick of suitable substrate material bymachining the brick into a shape suitable for use in the presentinvention. The crude block can be easily cut or sawed into a preformedshape, and then sanded, turned or machined into the final desired shaped“slug.” Although the composition of the substrate material is veryresilient to chemical, heat, thermal, and vibrational shock, thehardness is the substrate material is low. This low hardness permitsmachining with little or minimal amount of resistance or wear on tools.Despite the fact that the block has a low hardness and is soft, it isvery durable and easy to machine, sculpt, or shape. For example, incertain embodiments, a substrate material is, on a Moh's hardness scale,usually between 0.5 and 1.0 (or 1-22 on the Knoop hardness scale) withtalc being the softest at 1 (1-22 Knoop hardness) and diamond being thehardest at 10 (8,000-8,500 Knoop hardness). Other suitable valuesCertain prior art substrate materials are harder. For example, siliconcarbide has a Moh's hardness of 9-10 (2,000-2950 Knoop hardness).

With reduced effort compared to certain conventional substrates such ascordierite, the billet is shaped, sanded, turned, or machined, providingunlimited shaping capabilities of slug formation. The machining canrange from turning a cylinder on a lathe, sawing to shape with a keyholesaw, band saw or jig saw, sanding the shape or smoothing the surface, orany other method of machining commonly used on other solid materials andknown in the art. The billet can be machined down to very exactingtolerances with the same accuracy as machining metals, woods, orplastics. If the billet is cast in cylindrical molds with the desireddiameter of the final shape, the machining would simply require cuttingand sanding the cylindrical billet to the desired thickness. Thisprocess also reduces substrate loss due to excessive machining, andspeeds up the preforming process as well.

In certain embodiments, the frontal shape of the substrate is circular510, oval 520, and racetrack 530, as shown in FIG. 5. As is readilyunderstood, the shapes do not have to be exact. Three-dimensionally, thesubstrates may be in the form of a cylinder or a substantially flatdisc. Designs with squared corners, in certain applications, are not aseffective. Although easy to machine, square or angular designs haveproven to be a trap for rust and corrosives, e.g., road salt. Therefore,rounded corners are preferable on the frontal surface shape of the slugin certain embodiments.

The billet may be shaped by a band saw, jig saw, CNC, or other methodknown to one of ordinary skill in the art. The billet may be furthershaped by a hand rub, lathe sanding, belt sanding, or orbital sanding.Airborne particles are preferably vacuumed to prevent them from cloggingthe pores of the material. Further, these particles can enter thebearings of the drill press and destroy it, grinding away and scoringthe bearings. The ceramic dust is also very fine and can be easilyinhaled by operator.

In another embodiment, the present invention is directed to a method ofpreparing a catalytic or filtering substrate according to the presentinvention comprising preparing a billet of a nSiRF-C composite; andoptionally machining said billet to form a substrate of the presentinvention. If the billet is prepared in a shape suitable for use in oneor more processes of the present invention, the billet does notnecessarily need to be machined to a different shape. In this instance,the billet is prepared with a mold, as described below, having asuitable shape. Alternatively, the billet or substrate may be machinedto a suitable shape. Further, as described in more detail below, aplurality of channels are machined into the substrate.

The step of preparing the billet (or substrate) comprises known methodsof preparing these materials. Any known method of preparing a suitablebillet or substrate can be used. For example, suitable processes aredisclosed in U.S. Pat. Nos. 4,148,962 and 6,613,255, each of which isincorporated by reference herein in its entirety.

By way of a non-limiting example, in one embodiment, the steps ofpreparing a suitable substrate comprise:

heating a plurality of refractory silica fibers, refractory aluminafibers, and refractory aluminoborosilicate fibers;

mixing said fibers;

washing said fibers;

optionally chopping said fibers to one or more lengths;

blending or mixing the chopped fibers into a slurry;

adjusting the viscosity of said slurry, preferably by adding thickeningagent;

adding a dispersant;

adding the slurry to a mold;

removing water the slurry to form a green billet;

removing the green billet from the mold;

drying the green billet in oven, preferably drying at a temperature ofabout 250° F. to about 500° F.; and

heating, preferably prewarming and incrementally heating, the greenbillet in an oven at approximately 2000-2500° F.

As stated above, the billet is then optionally machined to form asubstrate of the present invention.

In another embodiment, the process further comprises machining aplurality of channels in the substrate.

In another embodiment, the process further comprises adding a washcoatto the substrate.

In another embodiment, the process further comprises adding a catalyticcoating to the substrate.

In a further embodiment, the mixing of the fibers is performed after thewashing and heating of the fibers.

In further embodiment, boron nitride is used in the process of making asubstrate of the present invention. BN=>B+N₂

In yet an additional embodiment, a thickening agent is used. Preferably,the thickening agent and dispersant used in the process aresubstantially removed from the substrate during a heating step. Forexample, the thickening agent and dispersant may be combusted during thesintering process.

The substrate 2510 is derived from a billet created by forming a rigidconfiguration of chopped and/or non-woven inorganic fiber and a bindingagent. The billet is machined or worked into the desired externaldimensions for the substrate 2510. The interior of the substrate 2510 isthen machined or worked to provide the desired surface area enhancementconfiguration, e.g., channels, washcoat, or catalyst. A durableinorganic hardened coating 2511 may be applied to the substrate 2510 bybrushing, spraying, dipping, or any other common application method. Inaddition, the substrate 2510 may include an oxidation or reductioncatalyst applied by brushing, spraying, dipping, or any other commonapplication method.

In one embodiment, the catalytic or filtering substrate of the presentinvention comprises a nSiRF-C; and a coating comprising, in admixture,silicon dioxide powder in an amount of from 23.0 to 44.0 wt %; colloidalsilicon dioxide in an amount from 25.0 to 45.0 wt %, water in an amountfrom 19.0 to 39.0 wt %; and one or more emittance agents selected fromthe group consisting of silicon tetraboride, silicon hexaboride, siliconcarbide, molybdenum disilicide, tungsten disilicide and zirconiumdiboride; wherein said coating has a solids content of from 45 to 55 wt%. Such a coating is disclosed in U.S. Pat. No. 5,296,288.

The present invention utilizes a plurality of high-grade non-wovensintered inorganic refractory fibers, such as those present in AETB.Other suitable materials for use as a nSiRF-C in the present inventioninclude: AETB-12 (having a composition of about 20% Al₂O₃, about 12%(14% B₂O₃, 72% Al₂O₃, 14% SiO₂; NEXTEL™ fiber), and about 68% SiO₂);AETB-8 (having a composition of about 20% Al₂O₃, about 12% (14% B₂O₃,72% Al₂O₃, 14% SiO₂ NEXTEL™ fiber), 68% SiO₂); FRCI-12 (having acomposition of about 78% wt. silica (SiO₂), and 22% wt.aluminoborosilicate (62% Al₂O₃, 24% SiO₂, 14% B₂O₃); and FRCI-20 (havinga composition of about 78% wt. silica (SiO₂) and about 22% wt.aluminoborosilicate (62% Al₂O₃, 24% SiO₂, 14% B₂O₃).

In a preferred embodiment, the components of the inorganic fibersconsists, or consists essentially of, fibrous silica, alumina fiber, andaluminoborosilicate fiber. In this embodiment, the fibrous silicacomprises approximately 50-90 (%) percent of the inorganic fiber mix,the alumina fiber comprises approximately 5-50 (%) percent of theinorganic fiber, and the aluminoborosilicate fiber comprisesapproximately 10-25 (%) percent of the inorganic fiber mix. The fibersused to prepare the substrate of the present invention may have bothcrystalline and glassy phases in certain embodiments.

Other suitable fibers include aluminoborosilicate fibers preferablycomprising aluminum oxide in the range from about 55 to about 75 percentby weight, silicon oxide in the range from less than about 45 to greaterthan zero (preferably, less than 44 to greater than zero) percent byweight, and boron oxide in the range from less than 25 to greater thanzero (preferably, about 1 to about 5) percent by weight (calculated on atheoretical oxide basis as Al₂O₃, SiO₂, and B₂O₃, respectively). Thealuminoborosilicate fibers preferably are at least 50 percent by weightcrystalline, more preferably, at least 75 percent, and most preferably,about 100% (i.e., crystalline fibers). Sized aluminoborosilicate fibersare commercially available, for example, under the trade designations“NEXTEL 312” and “NEXTEL 440” from the 3M Company. Further, suitablealuminoborosilicate fibers can be made as disclosed, for example, inU.S. Pat. No. 3,795,524, which is incorporated herein by reference inits entirety.

Additional suitable fibers include aluminosilicate fibers, which aretypically crystalline, comprising aluminum oxide in the range from about67 to about 77, e.g., 69, 71, 73 and 75, percent by weight and siliconoxide in the range from about 33 to about 23, e.g., 31, 29, 27, and 25,percent by weight. Sized aluminosilicate fibers are commerciallyavailable, for example, under the trade designation “NEXTEL 550” fromthe 3M Company. Further, suitable aluminosilicate fibers can be made asdisclosed, for example, in U.S. Pat. No. 4,047,965 (Karst et al.), thedisclosure of which is incorporated herein by reference.

In other embodiments, the fibers used to prepare the substrate of thepresent invention comprise α-Al₂O₃ with Y₂O₃ and ZrO₂ additions, and/orα-Al₂O₃ with SiO₂ added (forming α-Al₂O₃/mullite)

Various specific materials can be used to prepare the catalyticsubstrate. In one embodiment, the material used to prepare a substrateof the present invention comprises, or alternatively consists orconsists essentially of, refractory silica fibers and refractoryaluminumborosilicate fibers. In another embodiment, the material used toprepare the catalytic substrate comprises refractory silica fibers,refractory grade alumina fibers, and a binding agent, preferably aboronoxide or a boron nitride powder.

In one embodiment, the catalytic substrate of the present inventioncomprises, or alternatively consists or consists essentially of, analumina enhanced thermal barrier (“AETB”) material or a like materialknown to one of ordinary skill in the art. AETB material is known in theart and more fully described in Leiser et al., “Options for ImprovingRigidized Ceramic Heatshields”, Ceramic Engineering and ScienceProceedings, 6, No. 7-8, pp. 757-768 (1985) and Leiser et al., “Effectof Fiber Size and Composition on Mechanical and Thermal Properties ofLow Density Ceramic Composite Insulation Materials”, NASA CP 2357, pp.231-244 (1984), both of which are hereby incorporated by reference.

In another embodiment, the catalytic substrate comprises Ceramic tiles,such as alumina enhanced thermal barrier (AETB) with toughened unipiecefibrous insulation (TUFI) and/or reaction cured glass (RCG) coatings.Such materials are known in the art.

Another suitable material is Fibrous Refractory Ceramic Insulation(FRCI). In one embodiment, AETB is made from aluminaboriasilica (alsoknown as alumina-boria-silica, aluminoborosilicate, andaluminoboriasilicate) fibers, silica fibers, and alumina fibers. Onecommonly known application for AETB is as an exterior tile on the SpaceShuttle, ideal for shuttle re-entry. AETB has a high melting point, lowheat conductance, and coefficient of thermal expansion, ability towithstand thermal and vibrational shock, low density, and very highporosity and permeability.

In one embodiment, a first component of AETB is alumina fibers. Inpreferred instances of the present invention, the alumina (Al₂O₃ oraluminum oxide, e.g., SAFFIL), is typically about 95 to about 97 weightpercent alumina and about 3 to about 5 weight percent silica incommercial form. In other embodiments, alumina having a lower purity arealso useful, e.g., 90%, 92%, and 94%. In other embodiments, aluminahaving a higher purity are also useful. Alumina can be produced byextruding or spinning. First, a solution of precursor species isprepared. A slow and gradual polymerization process is initiated, forexample, by manipulation of pH, whereby individual precursor moleculescombine to form larger molecules. As this process proceeds, the averagemolecular weight/size increases, thereby causing the viscosity of thesolution to increase with time. At a viscosity of about ten centipoise,the solution becomes slightly adhesive, allowing fiber to be drawn orspun. In this state, the fiber may also be extruded through a die. Incertain embodiments, the average fiber diameter ranges from about one tosix microns, although larger and smaller diameter fibers are alsosuitable for the present invention

In one embodiment, a second component of an AETB is silica fiber. Silica(SiO₂, e.g., Q-fiber or quartz fiber), in certain embodiments, containsover 99.5 weight percent amorphous silica with very low impurity levels.Silica of lower purities, e.g., 90%, 95%, and 97%, are also useful forthe invention. In certain embodiments, an amorphous silica is used thathas a low density (e.g., 2.1 to 2.2 g/cm³), high refractoriness (1600degrees Celsius), low thermal conductivity (about 0.1 W/m-K), and nearzero thermal expansion.

In one embodiment, a third component of an AETB is aluminaboriasilicafibers. In certain instances, aluminaboriasilica fiber(3Al₂O₃.2SiO₂.B₂O₃, e.g., NEXTEL 312) is typically 62.5 weight percentalumina, 24.5 weight percent silica, and 13 weight percent boria. Ofcourse, the exact percentages of the constituents of thealuminaboriasilica may vary. It is largely an amorphous product but maycontain crystalline mullite. Suitable aluminaboriasilica fibers andmethods of making the same are disclosed, for example, in U.S. Pat. No.3,795,524, the teachings of which are herein incorporated by referencein their entirety.

Other suitable materials for use as a nSiRF-C in the present inventioninclude: AETB-12 (having a composition of about 20% Al₂O₃, about 12%(14% B₂O₃, 72% Al₂O₃, 14% SiO₂; NEXTEL™ fiber), and about 68% SiO₂);AETB-8 (having a composition of about 20% Al₂O₃, about 12% (14% B₂O₃,72% Al₂O₃, 14% SiO₂ NEXTEL™ fiber), 68% SiO₂); FRCI-12 (having acomposition of about 78% wt. silica (SiO₂), and 22% wt.aluminoborosilicate (62% Al₂O₃, 24% SiO₂, 14% B₂O₃); and FRCI-20 (havinga composition of about 78% wt. silica (SiO₂) and about 22% wt.aluminoborosilicate (62% Al₂O₃, 24% SiO₂, 14% B₂O₃).

In a preferred embodiment, the components of the inorganic fibersconsists, or consists essentially of, fibrous silica, alumina fiber, andaluminoborosilicate fiber. In this embodiment, the fibrous silicacomprises approximately 50-90 (%) percent of the inorganic fiber mix,the alumina fiber comprises approximately 5-50 (%) percent of theinorganic fiber, and the aluminoborosilicate fiber comprisesapproximately 10-25 (%) percent of the inorganic fiber mix.

Similar fibers to those fibers of AETB, as described herein, may beutilized in addition to or in the place of the AETB fibers.

Fiber production via melting can be performed in two general methods.The first method involves a combination of centrifugal spinning andgaseous attenuation. A glass stream of the appropriate viscosity flowscontinuously from a furnace onto a spinner plate rotating at thousandsof revolutions per minute. Centrifugal forces project the glass outwardto the spinner walls containing thousands of holes. Glass passes throughthe holes, again driven by centrifugal force, and is attenuated by ablast of heated gas before being collected.

In the second melting technique, molten gas is fed into a heated tankwhose bottom surface is perforated by hundreds or thousands of holes,depending on the application. Glass flows and is drawn through theseholes, forming individual fibers. The fibers are merged into strands andcollected on a mandrel.

In one embodiment, the AETB fiber mix in the slurry preferably comprisesthree ingredients including fibrous glass, alumina fiber, andaluminaboriasilica fibers. The fibrous silica will compriseapproximately 50-90 percent of the inorganic fiber mix; the aluminafiber will comprise approximately 5-50 percent of the inorganic fibermix; and the aluminaboriasilica will comprise approximately 10-25percent of the inorganic fiber mix. In other embodiments, the slurrycomprises any mixture of fibers that can be used make a substrateaccording to the invention as described above.

In a preferred embodiment, the fibrous component of the substrate is amixture of 64% amorphous silica, 21% alumina, and 15% aluminaboriasilicafiber, with trace amounts, e.g., 0.3 to 1.0 mg/m², of a surface activeagent employed to aid in the dispersion of bulk fiber in the slurryprior to and during casting.

In one embodiment, the fibers in the slurry are only primarily inorganicfibers. Preferably, in one embodiment, the present invention does notuse any carbon in formation of the substrate.

Alumina-zirconia fibers may be added to the inorganic fiber mix as afourth component or replacement component for other fibers.

Mix Fibers

In one step of an embodiment of the present invention, the fibers aremixed. Any number of known methods of mixing the fibers can be used tomix the fibers. An example is high-shear mixing which can be employed.

Heat Fibers

In one step of the present invention, the fibers are heated according toknown methods. The fibers are first heated to allow for the fibers to bemore evenly chopped. The heat-treated fibers are washed to remove all ofthe dust, debris, and loose particles, leaving only the fibers toprocess.

In a preferred embodiment, the fibers are heat cleaned

Wash Fibers

In one step of the present invention, the fibers are washed. In apreferred method, the fibers are washed so that the fibers aresubstantially free of dust and particles. In one embodiment, the silicafibers are washed in acid to remove impurities, rinsed, dried, andsubsequently heat treated to impart structural integrity.

Chop Fibers

In another step of the present invention, the fibers are chopped. Fiberfor use in the present invention can typically be obtained as bulk orchopped fiber. Methods of chopping fibers are known in the art. Mostmethods are continuous processes capable of handling multiple fibers orstrands simultaneously. Typically, the product is fed between a set ofrotating wheels or drums, one of which supports regularly spaced cuttingblades. As the fiber is drawn through the cutter, it is chopped tolength. Although specific manufacturing details remain proprietary forforming a blank from the chopped fiber, the art typically involves oneof two production mechanisms: melting and sol gel. Preferably, thefibers are heat treated before the final chopping.

Preferably, the fibers are then chopped to size. Suitable lengths of thefibers include, but are not limited to, about 0.1, 0.2, 0.3, 0.4, 0.5,or 0.6 inches. Other suitable lengths include ⅛″, ¼″, and ½″. It ispreferred that the fibers are relatively uniform in size. In anotherembodiment, the fibers that compose the catalytic substrate or thefiltering substrate are an average ¼ inch (approximately 1 hundredth ofa meter) in length and about one to 12 microns in diameter,alternatively, one to six, or 10 to 12 microns with a median fiberdiameter of three microns. In a preferred embodiment, particulatematerial is not added as it may clog pore space. Suitable fibers for usein the present invention are available commercially, e.g., from 3M. Ofcourse, in other embodiments, longer fibers are used.

Slurrying

In another step of the process of the invention, a slurry comprising thefibers is prepared. Rather than extruding a ceramic or wrapping a yarnor fabric around a perforated tube, the substrate may be made by acommon sol-gel process. This is accomplished by first pulling (via avacuum or gravity-drawn) a well mixed sol of inorganic fibers andcolloidal solution into a fiber mold which creates the sol blank orgreen billet or billet.

Alternatively, a squeeze-cast pressurizing process may be used wherepressure is reduced to negative value or a vacuum process. The vacuumprocess allows the inorganic fiber blank to be formed with super lowdensities while maintaining its strength. The sol-gel process inconjunction with the pressurized process or vacuum process helps toproduce exceptionally low densities, which is extremely beneficial tothe filtration of particulates.

The fibers are blended together in a slurry. In certain embodiments, aslurry may contain 1 to 2 weight percent solids and is nearly as fluidas water. Alternatively, the slurry may contain from about 0.5 to about5 weight percent solids. Other weight percentages are acceptable aswell, as is known in the art.

The chopped fibers are mixed together in a slurry using a high-shearmixer. Preferably, deionized water is used in the slurry to avoidimpurities that may act to flux or destabilize the fiber in service. Inone embodiment, the slurry can be pumped through a centrifugal cycloneto remove shot glass and other contaminants, including high sodaparticles.

Alternatively, organic fibers or particulate may be added to the fiberslurry in proportions up to thirty percent by weight. During the firingstage of production, the organic fiber is volatilized or burned out ofthe article. Burning the fiber leaves a void that allows a path forgases to escape. By varying the type and proportion of polymeric fiber,the permeability of the tile can be tailored.

Adjusting Viscosity

In another embodiment, viscosity is adjusted to a suitable range. Ahigher viscosity prevents fibers from “laying down,” i.e., laying flator becoming oriented only in a substantially horizontal direction. Boronnitride may be added as a thickening agent to coat the fibers inpreparation for high-strength sintering. In one embodiment of thepresent invention, boron nitride is added and aluminaboriasilica fiberis not utilized in the slurry.

Adding Dispersant

In one embodiment, the process comprises adding one or more dispersantsto the mixture or slurry.

In one embodiment of the present invention, one or more surface activeagents are added to the slurry during the process of the invention. Thesurface active agent is used in quantities of about 5 to about 10 weightpercent. The surface active agent is employed to aid in the dispersionof bulk fiber in the slurry prior to and during casting to prevent thefibers from bundling together.

In one embodiment of the present invention, one or more catalysts asdescribed above are added to the slurry. By adding a catalyst at thisstage of the process, a substrate having the catalyst impregnated withinthe porous material is made. In one embodiment, this configurationeliminates the need for further washcoating or catalyzing.

Molding

In one embodiment, the slurry is poured into a mold to form a billet.The shape of the mold may take any shape desired. In certainembodiments, the shape of the mold will produce a substrate having ashape suitable to be used in a catalytic converter or particulatefilter. For example, the mold may be in the shape of a cylinder.Alternatively, the mold is in the shape of a pentagon. Preferably, theslurry is not allowed to settle in the mold because the fibers may laydown. In one embodiment, a vacuum suction method is employed to keep thefibers from settling down and to maintain uniform porosity and densityof the material throughout the billet. The vacuum suction technique maybe employed from any number of directions to control the fiberarrangement and density with the green billet.

By way of example, a billet of the material of the catalytic orfiltering substrate is produced in a mold of 24 inches by 24 inches (576in²)×4 inches having rounded corners. Of course, billets may be producedof larger or smaller sizes.

The material of the mold can be any material that is stable with water,including but not limited to, metal or plastic. Other suitable materialsinclude aluminum, PLEXIGLAS, and other synthetic materials. Aluminum isvery durable over the long term whereas PLEXIGLAS material is cheap andeasy to machine. Suitable permeable surfaces are available in the formof a fine metallic mesh screen. Semi-permeable surfaces larger thanabout 50 in² may under certain circumstances preferably use a backing orsupport structure to prevent sagging.

There are embodiments in which an anaerobic, i.e., oxygen free,environment may be desirable during casting. The oxygen-free atmospherecreates an environment which minimizes metal oxidation and uniquelystrengthens the fiber bonds. The soaked billet is placed into a chamber,e.g., a large plastic bag, filled with ammonia gas. Ammonia is mostcommonly used because of its low cost and availability. Nitrogen and/orhydrogen gas may also be introduced. Nitrogen is preferred to hydrogen,since hydrogen is volatile. In fact, any gas may be introduced as longas a reducing and oxygen free environment is maintained. Preferably, thegas is provided at a constant flow until the soaked sol billet hasformed into a gel billet. At that point, the gas is turned off and thegel billet is exposed to the open air, allowing the gases to escape.

Carbon or organic-based shape-formers may be used as hole-forming rodswhich are introduced into the green billet during the molding stage.Upon high temperature sintering, these rods may disintegrate and leavebehind the desired plurality of channels.

Dewatering the Slurry

In one embodiment of producing the billet, the slurry is placed in theenclosed mold where at least one dimension is adjustable and at leastone wall is semi-permeable. Compressive force is applied via theadjustable wall and water is expelled from the slurry via thesemi-permeable wall where fiber collects and felts. Compression iscontinued until the desired preform, i.e., billet, dimensions areachieved. This method is generally limited to simple geometries likeblocks or cylinders.

Gravity is typically not a sufficient driving force, therefore requiringthe use of a vacuum pump. The vacuum pump uses very little to nopressure. In some instances, a vacuum is employed to dewater, but thesuction using is very slight. The vacuum is used as a means to speed upthe drying process with great sensitivity to avoid increasing thedensity. Preferably, only mild vacuum assistance is used.

More complicated-shaped billets can be prepared by an alternativemethod, for example, in which a head of slurry is placed and maintainedover a semi-permeable mold form. Low pressure is established outside thepermeable form via the vacuum pump. The differential pressure driveswater through the permeable form where fiber collects and felts. Thedifferential pressure is sustained until the desired thickness isachieved. This process is suited to applications where the desiredsubstrate is highly curved, as billets can be produced near-net-shape orclose to their final form.

Injecting or mixing multiple (two or more) slurry recipes and varyingthe vacuum rate of pull (a plurality of times) provides a billet withsome areas denser than others and/or areas with different physicalproperties. The billets can have graduated or different layers or coreswith different chemical compositions and densities. The billets can haveone or a plurality of zones, each with a unique shape, location, andphysical properties as needed. Each zone can change as needed forchanging the strength, heat or electrical conductivity, catalystadhesion capability, thermal expansion, vibrational or thermal shock,weight, porosity and permeability, sound dampening, or any otherpreferable property.

By using different slurry recipes and molding techniques, the billetscan also be layered. In addition, the billet is not restricted only toparallel planar layers, such as layers on a cake, but the billets can beformed with horizontal, angled, spherical, pyramidal, and free-formlayers, or any other configuration known in the art. It should also benoted that the density of the billet could be chemically and physicallyaltered, if desired, during this process.

The billets can also be formed by placing a plurality of billets, ofdifferent chemistry and in any configuration, whether cured or uncured,inside or within another billet. The core billets can be manually placedinto the billet or injected into the core. The result is a core or aplurality of cores of less or more density. The shape or form of thesecores and billets is unlimited as is the combination of layering thecores. Cores may even be created inside cores. The process can berepeated an unlimited number of times as needed yielding a unique numberof combinations of billets in unlimited shapes.

Drying the Green Billet

In one step of an embodiment, the slurry in the mold is oven-dried longenough to dewater, i.e., drive off any water it may contain. Water canbe drained out by gravitational forces. Slight vacuum assistance may beutilized. Other methods known in the art can of course be used.

Remove Green Billet from Mold and Drying Green Billet

In one step of an embodiment of the invention, the green billet isremoved from the mold. Generally, the billet can be removed when it isdry enough to handle. Alternatively, the billet is removed when it isdry enough to be manipulated by a machine.

For example, when the billet is dry enough to be handled, it is removedfrom the mold. The billet is then dried in an oven. A low enoughtemperature is used so as to complete dewatering process and permitfibers to remain substantially in their intended configuration. Mostpreferably, the temperature is sufficient to dry the billet as requiredbut insufficient to cause any or substantially any sintering of thebillet. In another preferred embodiment, a temperature of about 250 to500 degrees Fahrenheit is used in this step. In a further embodiment,the billet is dried at a temperature of about 180° C. for about 2 toabout 6, preferably about 4 hours. Other times and temperatures as areknown in the art may be used.

A dried billet is then optionally soaked in a sol-gel binder, preferablyan alumina sol gel binder, for a period of time, e.g., a few days, atvarious temperatures, as is known in the art, as the billet “wicks”(i.e., soaks up) the binder solution into the billet. A suitable binderis known in the art and may be required to impart preform structuralintegrity as well as to promote sintering. The billet may utilize asingle or multiple binder process to vary the strength and conductivityof the billet. Applying a binder several times will increase thestrength of the billet but may also reduce or plug up the pore spaces.Any suitable binder may be used. The binder may be an oxide binder suchas SiO₂ or Al₂O₃. The oxide binder may also be a glass configuration, acrystalline configuration, or other inorganic binder. A binder may beapplied using known techniques and methods, such as those disclosed inU.S. Pat. No. 3,549,473, the teachings of which are incorporated hereinby reference in their entirety.

Drying the Green Billet (Sintering)

In another step of an embodiment of the present invention, the greenbillet is heat cured. The temperature for heat-curing, or sintering, isgenerally a higher temperature than that used for drying the greenbillet. In one embodiment, the temperature is incrementally increasedover one or more hours, preferably several hours, until the desiredtemperature is reached. In one embodiment, the oven is pre-warmed andincrementally heated to approximately 2000-2500° F. Other temperaturesknown in the art are suitable.

In a preferred embodiment, after gelling the binder, the billet is curedby heating the billet to about 200 degrees Fahrenheit for about fourhours, and then slowly increasing the temperature to about 600 degreesFahrenheit over about a five hour period. After achieving andmaintaining the maximum temperature, the billet is quickly quenched. Theend result is a rigid inorganic fiber billet. Once again, the process ofheat curing the blanks can vary in the temperatures used, length of timeto cure, the temperature and time of quenching, the temperatureincremental increases, and the incremental temperature increase timing.

Billets are fired to supply the necessary energy to sinterfiber-to-fiber contacts, thereby forming bonds that impart strength tothe substrate. For example, strength can be increased by increasing thenumber of fiber-to-fiber contacts. Increasing the number of contactsincreases density and tortuosity. The more tortuous a pore networkbecomes, the lower the permeability. Sintering does not cause the fibersto melt together, but instead binds them chemically. The billet isprogressively heated in a high temperature furnace. The billet ispre-warmed and then incrementally heated to approximately 2000 to 2500degrees Fahrenheit until a desired density and fusion are obtained.Secondary chemicals such as the thickening agent are combusted away inpreferred embodiments. A substrate comprising, or alternativelyconsisting of or consisting essentially of, the sintered fibers remains.

In a preferred embodiment, the viscosity (thickening agent) chemicalsand dispersant are combusted away.

In other embodiments, multiple curing steps are performed. This can bedone to increase hardness of the substrate.

The variables in the drying and curing processes can be adjustedaccording to the desired density, strength, porosity, or permeability,or resistance to high temperatures, of the fiber blank. In certainembodiments, the curing process can use a plurality of curingapplications and can vary the heating and cooling intervals andapproaches. The billet can also be rapidly cooled to quench or temperthe billet. The slurry may undergo additional heat or other treatments,such as densification coatings or multiple curing and sintering.

Physical Modification

In certain embodiments of the process, the billet is coated with acatalyst. In one method of applying catalysts to a substrate, thesubstrate may be formed from a slurry that contains catalysts. Othersuitable methods of applying a catalyst may be used. Another advantageof the present invention is that it has been surprisingly discoveredthat a catalyst can be applied to the nSiRF-C material using methodsthat can apply catalyst to other materials.

In another embodiment in the present invention, catalyst is added to theslurry prior to molding. In this instance, a catalytic substrate isformed having the catalyst reside directly onto the individual fibersthat constitute the substrate. This method of adding catalyst to thesubstrate, in certain embodiments, provides an efficient method ofdispersing catalyst into the core of the catalyst substrate and not havethe catalyst reside only along the channel walls. In this embodiment, awashcoat is not necessary.

Machining

A billet in the form of a crude block can be cut or sawed into aspecified shape, and then sanded, turned or machined into the finaldesired shaped “slug.” Although the composition of the material is veryresilient to chemical, heat, thermal and vibrational shock, in preferredembodiments, the hardness is very low. This low hardness permitsmachining with little or a minimal amount of resistance or wear ontools. Despite the fact that the billet in certain embodiments has a lowhardness and is soft, it is very durable and easy to machine, sculpt, orshape. On a Moh's hardness scale, the material is usually between 0.5and 1.0 (or 1-22 on the Knoop hardness scale)—with talc being thesoftest at 1 (1-22 Knoop hardness) and diamond being the hardest at 10(8,000-8,500 Knoop hardness). For example, silicon carbide has a Moh'shardness of 9-10 (2,000-2950 Knoop hardness). In relation to other knownsubstances, the billet is very soft and effortless to machine or sculptas Styrofoam or Balsa wood.

The billet can be shaped, sanded, turned, or machined, providingunlimited shaping capabilities of slug formation. The machining canrange from turning a cylinder on a lathe, sawing to shape with a keyholesaw, band saw or jig saw, sanding the shape or smoothing the surface, orany other method of machining commonly used on other solid materials andknown in the art. The billet can be machined down to very exactingtolerances with the same accuracy as machining metals, woods, orplastics. If the billet is cast in cylindrical molds with the desireddiameter of the final shape, the machining would simply require cuttingand sanding the cylindrical billet to the desired thickness. Thisprocess also reduces substrate loss due to excessive machining, andspeeds up the preforming process as well.

There many possible frontal and rear surface shapes including circular510, oval 520, and racetrack 530, as shown in FIG. 5.Three-dimensionally, the substrates may be in the form of a cylinder ora substantially flat disc. Conventional substrates exist as one of thesethree designs. Designs with squared corners are not as effective.Although easy to machine, square or angular designs have proven to be atrap for rust and corrosives, e.g., road salt. Therefore, roundedcorners are preferable on the frontal surface shape of the slug.

The billet or substrate or slug may be shaped by a band saw, jig saw,CNC, or other method known to one of ordinary skill in the art. The slugmay be further shaped by a hand rub, lathe sanding, belt sanding, ororbital sanding. Airborne particles must be vacuumed to prevent themfrom clogging the pores of the material. Further, these particles canenter the bearings of the drill press and destroy it, grinding away andscoring the bearings. The ceramic dust is also very fine and can beeasily inhaled by operator.

The shaped slug is utilized as a substrate in the present invention. Thesurface area of the substrate is an important characteristic forcatalysis application. Surface area is the sum amount of surface thatexhaust emissions must pass across when traveling through an exhaustfilter. Increased surface area translates into more room for chemicalreactions to take place between pollutants and catalytic and thermalprocesses, making a catalytic converter process quicker and moreefficient. Speed and efficiency can result in little to no clogging,which can cause failure of the exhaust system.

In one embodiment, the substrate of the present invention has a grosssurface area of 83.58 square inches per cubic inch. This translates intoa much higher area that can be impregnated with precious metals, ascompared to the cordierite samples having comparable macrodimensions(e.g., diameter, length and width). Note, however, that this grosssurface area calculation does not even include the density, porosity,and permeability of the different materials.

In one exemplary embodiment of the present invention, the substrate isused in an exhaust filter system for a diesel engine. The substrate iscreated using AETB formulation and formed in approximately 13″×13″×5″billets with a density between 8 and 25 pounds per cubic foot. From thebillet, a five inch tall cylinder slug which is six inches in diameteror an oval right-cylinder slug is cut from the billet using a diamondtipped or tungsten-carbide band saw. This slug is further machined toexact tolerances on a spinning lathe (for right circular cylinders) oron a belt sander forming the substrate.

Preparing Holes and Channels in Substrate

In an embodiment of the present invention, a plurality of channels areformed in the filtering or catalytic substrate substantiallylongitudinal to the intended gas flow. The channels extend through thelength of the substrate, either partially or fully. FIGS. 5-14 showschematic diagrams exemplifying certain embodiments of the presentinvention having a plurality of channels. In certain embodiments, thechannels extend at an angle to the flow of fluid.

The inside surfaces of these channels can be chemically coated so as tocapture and treat more pollutants in a small volume of substrate. Whenchannels are formed in the substrate, smaller diameter channels, e.g.,small channels having 200, 400, 500, 600, 700, 800, 900, 1000, 1100,1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300,2400, or 2500 cpsi, are preferred to retain a high surface area.

In another embodiment, the channels extend through the entire length ofthe substrate. Such a substrate has a flow through configuration.

Alternatively, the channels do not extend through the entire length ofthe substrate but extend from about 50% to about 99% through the lengthof the substrate. Such a substrate is considered a wall-flowconfiguration. The undrilled portion remaining in the channels of thewall-flow substrate may have a varied thickness. FIG. 8 shows awall-flow pattern substrate 820 according to an embodiment of thepresent invention with an undrilled portion 840, 845 of varied wallthickness. In this embodiment, alternating entering channels have awider wall thickness than other entering channels as well as the exitchannels. However, the varied undrilled portion thickness may beconfigured in any combination such that the entering or exit channelshave a thinner or thicker undrilled portion, and wherein the all of theundrilled portions may or may not be substantially similar in thickness.The wall thickness is so thin and porous that the exhaust gas 830 passesfrom emission entering channels through the walls into exit channels,trapping emission particulate. The length between the inner edges 850and 855 of the undrilled portions is known as a crossover region. Wherethe undrilled portion 840 is thicker in some or all entering channels,emission flow 830 is likely to go through the channel walls of thesubstrate in the crossover region and exit the substrate 820. Theemission flow 830 may still pass through thinner undrilled portion 845.In another embodiment of the present invention, the undrilled portion ofthe channel has a selective impregnation of catalysts, such that theamount of catalysts differs from that on the channel walls.

The thickness of this undrilled portion is limited. Gas flow increasesby increasing the surface area of the walls with equivalent thicknesses.If the undrilled portion is too thin, it could rupture from excessivebackpressure.

Mechanical Drilling

Once an embodiment of a substrate is cut from the billet and machined,it can be inserted into a drilling holder for drilling. A plurality ofchannels can be drilled into the substrate in the directionsubstantially parallel to the major axis of the cylinder and the flow ofexhaust emission. The smaller the channel diameter, the more channelscan fit into the substrate.

In an alternative embodiment, channels are drilled into a substrate. Thesubstrate is placed in a metal holder for drilling. The holder can befor example a pair of large metal arms that firmly holds the substrateslug in place and keeps it from moving while not crushing the substrate.The holder engages the substrate and holds it steady for drilling. Afterdrilling one side of the substrate, the holder rotates precisely 180degrees to allow for drilling in the opposite side of the substrate. Ifthe rotation is not precisely 180 degrees, the drilled channels will notbe properly aligned or parallel. Further, the pressure at the ingressneeds to be substantially identical or similar to the pressure at theegress. Preferably, in order to ensure parallel walls, the holder mustnot move the substrate in an more than 0.0001 inches in any unwanteddirection.

The channels of the substrate of the invention can be prepared using amechanical drilling process. In one embodiment, computer number control(“CNC”) drilling is used, which is common among machine shops and is thepreferred method. CNC drilling is much slower and is not as economicallyfeasible in mass manufacturing environments requiring production ofthousands of filters per day. CNC drilling performs with high precisionand accuracy. CNC drilling is done by making multiple passes with thedrill bit. The CNC drills a little further into the substrate on eachpass, removing fibrous material as the bit comes out.

The drill bit can be tungsten carbide due to its tough and brittlenature, or can be a similar material known to one of ordinary skill inthe art.

The drill bit penetrates at a feed rate of about ten feet per minute.The slow feed rate is necessary in order to prevent the drill bit frommelting. When the drill bit penetrates at a feed rate of twenty-fivefeet per minute, the drill bit melts. Also, due to the tremendous porespace, the drill bit has a tendency to “walk” or move around. A slowerpenetration rate cures this problem.

Rotating the drill bit at a slow rate is preferable. The drill bitshould rotate at approximately 200 revolutions per minute. Rotating thedrill bit at higher rate, such as about 10,000 revolutions per minute,may cause the drill bit to melt. The drill bit is kept cool throughoutthe drilling with lubrication such as water, alcohol, or glycerin.

Once the substrate is cut and sanded to final dimensions, channels arecut or drilled into the substrate. In this exemplary embodiment, thechannels are cut using a DPSSL. Since the substrate is so porous andpermeable, the substrate does not need to as thick as conventionalfilters. In addition, thinner or smaller substrates are less costly toproduce because cutting one billet can produce multiple substrates andrequires a reduced amount of any coatings or catalysts to be applied.

Water Drilling

In another embodiment, water cutting (or water drilling) is used forforming channels. Water cutting uses a fine spray of water with veryhigh pressure and cuts holes in the substrate. However, the water jetcannot be stopped during the cutting process to leave a blind hole(i.e., a channel that does not go through the substrate completely). Thephysical characteristics of the water jet limit the size of the channelopening to a diameter no smaller than the diameter of the jet. Incertain embodiments, a rectangular hole could be created with the jet.

Gas-Drilling

In another aspect of the invention, a gas drilling method is used toprepare the substrate. Gas-drilling is known in the art and can beapplied to substrates of the present invention to prepare channels inthe substrate.

Combing

In another embodiment, the channels are formed or shaped using a combprocess. The comb is a preferably a metal device with a plurality oftines that can be forced into (e.g., broaching) the substrate. The combsused for broaching comprise a plurality of tines. Tine length, width,thickness, and shape may be varied according to the desired properties,configurations, and dimensions of the channels.

In certain embodiments, the comb is forced into the substratesubstantially perpendicular to the surface of the substrate. In otherembodiments, the comb is forced into the substrate at an angle to thesurface of the substrate. Using a comb is a preferred method, inparticular for forming blind channels. It is understood that a suitablecomb can also be made so that the comb is made of a rows and columns oftines e.g., 4×4, or 16 by 16.

In general, the comb process comprises repeatedly forcing the comb intothe substrate material a plurality of times until most or all of thechannel is shaped. This process is referred to herein as pecking.Optionally the comb may be removed from the channel after each forcinginto so that excess substrate material can be cleared from the channelby, for example, air. It is preferable to prevent fiber build-up duringthe pecking/broaching steps. Fiber build up may cause walls to ruptureor the entire. To manage this property, a vacuum and/or compressed aircan be employed to clear the channels and drill bit surfaces.

In one embodiment, the comb is forced into the substrate with a forcesufficient to displace or dislodge an amount of substrate material fromthe channel wall. In a preferred embodiment, a sufficient amount offorce is applied to the comb so that the tines extend about 0.1 inchesinto the channel. Other suitable values include 0.05 0.15, and 0.2.Preferably, the amount of force applied to form or shape the channels isan amount sufficient to form or shape the channel without substantiallydamaging the channel wall. The process comprises forcing the tines intothe substrate repeatedly until the channels is produced of desiredlength and shape.

The shape of the tines dictates the shape of the channels. For example,a rectangular-shaped tine on the comb is used to create rectangularshaped channels with a rectangular shaped channel opening.

A wedge-shaped tine on the comb is used to create wedge-shaped channels.Utilizing a wedge-shaped tine produces channels wherein the walls areparallel with a square-shaped opening. As shown in FIG. 17, a substrate1700 incorporates parallel wedge-shaped “blind” channels 1702, i.e.,channels with no exit hole. The blind channels 1702 force gases 1704 topass through the pore space channels walls prior to exit.

A four-sided pyramid-shaped tine on the comb is used to create apyramidal-shaped channel. The walls are parallel and opening issubstantially square-shaped. However, the wall thickness at the channelopening is minimal as the channels meet at a point, rather than beingadjoined by a wall with a flat front. This results in a decrease infrontal surface area, and thus a decrease in backpressure. Withfour-sided pyramid-shaped shaped tines, shims are not needed to separatethe combs. In this embodiment, with reference to FIG. 16, a suitablecomb has tines which come to a point rather than have a flat end. Ofcourse, various other shapes of tines are encompassed by the presentinvention.

A tent-shaped tine on the comb is used to create a polygonal-shapedchannel. Frontal surface area is minimized with polygonal-shapedchannels.

Referring to FIG. 16, the dimensions of an exemplary comb 1600 are shownaccording to an embodiment of the present invention. The comb 1600 isapproximately 6.000 inches long and 0.0308 inches wide. The comb 1600comprises a base 1610 from which a plurality of tines 1620 extend. Thebase 1610 is 0.4375 inches high. The plurality of tines 1620 are 1.250inches long and 0.0308 inches wide, and spaced by 0.010 inches.

In one embodiment of the comb process, the channels are first formed bya drill bit and are circular. In order to produce shaped channels withparallel walls, according to one embodiment of the present invention,tines of combs broach (i.e., press or stamp) the circular channels tocreate the shaped channel. An embodiment of a comb 1500 is shown in FIG.15. Preferably, broaching is done on a CNC press. The impression leftbehind is shaped channels and channel openings. The cell wall thicknessmay be varied as described above. In certain embodiments, the combingprocess produces a catalytic or filtering substrate having a channelwall thickness of about 4 mils to about 20 mils, preferably about 6 milsto about 10 mils.

In the comb process, metal combs may be placed in a box called a jig andmounted in the CNC press for broaching. Within the jig, the combs areseparated by shims. The spacing between the combs is a low tolerance,requiring the combs to be held tightly in the jig to restrict movementduring broaching. Referring to FIG. 16, a shim 1630 is utilized as aspacer for comb 1600. Shim 1630 has dimensions of 0.010 inches wide,6.000 inches in length, and 0.4375 inches high.

Preferably, at least one screen is provided over the combs to keep thetines aligned. Preferably, the screens are floating to distributealignment as needed. Additionally, the screens are helpful for tines ofvarying lengths, for example from about 0.5 inches to about 6.0 incheslong. The at least one screen may be located anywhere along the tines,such as floating, spring-loaded, or fixed. The at least one screen maybe floating along the tines. The tines are not affixed to the at leastone screen, rather the screens are placed on the tines such that thescreens are adjustable. The at least one screen may be spring-loaded onthe tines. By spring-loading the screen, the pressure of the substrateagainst the screen maintains the distance between the tines atapproximately the edge of the substrate. The at least one screen mayalso be fixed to the tines, at any position along the length of thetines.

Another embodiment of the present invention is directed to a process ofpreparing a catalytic or filtering substrate having a plurality ofchannels, comprising using a comb to peck at the substrate to form theplurality of channels. This process, in preferred embodiments, is astepwise process. That is, the entire channel is not formed with oneinsertion of the tine of the comb. Rather, the tines of the comb arerepeatedly inserted and removed in small increments until the desiredlength of the channel is obtained. Preferably, the channels are clearedof dislodged substrate material between each peck or every other peck

In another embodiment, the comb process is an automated processutilizing machines and/or robots to form the channels.

Method of Making Combs

There are a number of methods of making combs for use in the presentinvention. The combs may be made of a material including, but notlimited to, stainless steel, tungsten, or key stock. Methods of shapingthe comb include laser cutting, water cutting, and electronic dischargemachining, or utilizing other shaping methods available to one ofordinary skill in the art.

DPSSL may be used to manufacture combs. Water cutting may also beemployed to manufacture the combs. For example, thirty to forty combsare made with one cutting using a water cutting process in oneembodiment.

Electronic discharge machining (“EDM”) is an alternative method tomanufacturing combs. EDM is a thermal erosion process whereby conductivematerial is removed by a series of recurring electrical dischargesbetween an electrode and a conductive workpiece, in the presence of adielectric fluid. EDM may similarly be used on the substrate if thesubstrate is made electroconductive. There are at least two types ofEDM: (1) ram and (2) wire.

Using the EDM ram, i.e., die sinking, an electrode/tool is attached to aram which is connected to one pole, usually the positive pole, of apulsed power supply. The workpiece is connected to the negative pole.The workpiece is then positioned so that there is a gap between theworkpiece and the electrode. The gap is then flooded with the dielectricfluid. Once the power supply is turned on, thousands of direct current,or DC, impulses per second cross the gap, beginning the erosion process.The spark temperatures generated can range from 14,000 degrees to 21,000degrees Fahrenheit. As the erosion continues, the electrode advancesinto the work while maintaining a constant gap dimension.

Preferably, the wire EDM method is preferred for comb manufacture. Thewire method uses a consumable, electrically charged wire as an electrodeto make intricate cuts as it moves in preset patterns around theworkpiece.

When walls are too thin, any rough edges on the tines may tear the wallsentering or exiting during broaching. Accordingly, the combs are bepolished to remove any burrs or sharp edges that could catch on thefibers. Cutting and polishing the combs can generate heat, which maywarp the comb. A tolerance is preferably maintained of approximately0.0001 inches in order to insure the hole generated is parallel and notruptured.

The combs used for broaching comprise a plurality of tines. Tine length,width, thickness, and shape may be varied according to the desiredattributes of the channels. Referring to FIG. 16, the dimensions of acomb 1600 are shown according to an embodiment of the present invention.The comb 1600 is approximately 6.000 inches long and 0.0308 inches wide.The comb 1600 comprises a base 1610 from which a plurality of tines 1620extend. The base 1610 is 0.4375 inches high. The plurality of tines 1620are 1.250 inches long and 0.0308 inches wide, and spaced by 0.010inches.

Laser Machining

Other methods include diode-pumped solid-state laser (“DPSSL”) drilling;chemical lasers, e.g., CO₂; electron beam (“EB”) drilling; or electrodedrilling machines (“EDM”), or utilizing other methods known to one ofordinary skill in the art. Any laser suitable for cutting the materialof the combs may be used.

The substrate may be cut using laser drilling, such as DPSSL drilling.This method drills with a laser programmed using a CAD program. The CADprogram is loaded into a CAM program. The laser cuts with oxygen or,preferably, nitrogen in fine pulses. The DPSSL allows channels to be cutat a rate of about 2,000 channels per minute. In one embodiment, thechannels have an approximate diameter of 100 nanometers. Laser drillingmay be employed using known techniques and methods as disclosed in U.S.Pat. No. 4,686,128, the teachings of which are incorporated herein byreference in their entirety. In one embodiment, the process uses laserdrilling to prepare channels having a depth (or length) of about 0.5inch or less.

In one embodiment, the channels produced are large enough for theparticulates to enter but small enough that the majority of theparticulates are removed from the exhaust gas flow.

In addition, in one embodiment, the substrate material is aboutninety-seven porous, which means that there is a tremendous amount ofroom for gases to pass through the substrate. This large porosity alsoprovides an additional surface area for the particulate to deposit onto.

Pulsed Lasers Gator Series G355-3 G532-5 G532-10 Wavelength 355 532 1064nm Average Output Power ¹⁾ 3 5 10 W Pulse Repetition Rate ²⁾ 0-15,0000-15,000 0-15,000 Hz Pulse Energy ¹⁾ 0.3 0.5 1 mJ Pulse Duration (FWHM)¹⁾ 15 ± 3 15 ± 3 15 ± 3 ns Beam Diameter (1/e²)¹⁾ 1.0* 1.0 0.7 mmSpatial Mode TEM₀₀ TEM₀₀ TEM₀₀ M²¹⁾ <1.2 <1.2 <1.2 ¹⁾Measured at 10 kHzrepetition rate; ²⁾Externally triggered from 0-15.000 Hz (attenuatedpower). Internally tiggered from 7500 Hz to 15,000 Hz. Real RandomFiring Mode for external triggering between 0 and 15,000 Hz in fullpower mode is optional; ³⁾Gator lasers utilize a colsed loop watersystem for temperature control..

Preferably, the substrate material is substantially free of impurities,such as carbon, when being machined by a laser.

Molding Holes

In an alternative embodiment, the substrate of the present invention isprepared with channels preformed in the billet. In this embodiment, theuse of channel formers produces channels in the billet. The channelformers are rods having a suitable size and shape to form a desiredchannel when the green billet is formed.

Various types of material can be used for said channel formers. Forexample, the channel formers may be a strong durable material, such asmetal or polymer that is able to withstand the temperatures of thedrying process. Once the green billet or the final billet is formed, therods are removed to leave the channels. The channels may be furthermachined as described above.

Alternatively, in other embodiments, the rods are made of a materialthat can evaporate or disintegrate upon exposure to a suitable source ofradiation or heat, such as laser or heat. In another embodiment, thechannel formers are made of carbon, carbon derivatives, or the like.

Specific Embodiments

In certain embodiments, the channels are drilled using a CNC drill,which is computer controlled to maintain uniformity, as described below.The drilling process is performed under a constant water shower toprevent dust from becoming airborne, which is an OSHA hazard, and mayget into the bearings of the drill and destroy it.

The drilled substrate is optionally oven dried to drive or bake off anywater or other liquid that may reside in the pore space before anycatalytic applications. Baking time is not critical. A sufficient timeis used to remove the majority or substantially all water. Evaporationof the water can be determined by simply weighing the substrate. Bakingtime primarily speeds up the dewatering process. After heating thefilter element for several different intervals, the weight will leveloff and the substrate is ready for any catalyst or coating application.

In a preferred embodiment, the channels of the substrate are firstprepared by drilling and then shaped using the comb method. Due to thelow heat conductance nature of preferred substrates, when the substrateis drilled, most heat generated during drilling and cutting process isreflected back at the drill bit and away from the substrate. For thisreason, the drill bits may absorb some of the heat and expand, overheat,and/or melt. Preferably, cooling the drill bit is performed, preferablywith water. In another embodiment, the drill operated at a reduced drillspeed, e.g., 200 RPM, to minimize the generation of heat. Of course,other drill speeds, both faster and slower are suitable. In anotherpreferred embodiment, the drilling uses two or four or six faceteddrills with modified twists and head (drill tip) configurations

Additionally, in a preferred embodiment, the channel is drilled over aplurality of drilling attempts. For example, a channel that is about oneinch in length may be prepared by drilling into the substrate at depthsof about 0.1 inch at a time until the final length is attained. Thechannel can be cleared of drilled substrate material between drillingattempts.

In one embodiment, a pecking methodology is utilized because vacuumingof cut fibers must be removed.

In a preferred embodiment, the blind channels were drilled a fractiondeeper than our intended depth to allow the fibers to be packed intothat extra area during the combing process. The combs were programmed togo the depth of the wall flow configuration indicated and that extravoid accommodates any loose substrate material remaining in thechannels.

Product by Process

In another embodiment, the present invention is directed to a productprepared according to the process described herein. Specifically, theinvention is directed to a catalytic substrate prepared according to anyone of the specific embodiments described herein. In another aspect, thepresent invention is directed to a filtering substrate preparedaccording to any one of the specific embodiments described herein.

Applications

Various embodiments and applications of the invention are discussedbelow. These example applications are discussed for illustrativepurposes only and are not limiting of the scope of the invention. Any ofthe embodiments of the catalytic substrate and filtering substratedescribed above can be used in the various applications.

Catalytic Converter

In another embodiment, the present invention is directed to a catalyticconverter comprising a catalytic substrate of the present invention. Thecatalytic converter of the present invention can be used in an engineexhaust system in a similar manner in which known catalytic convertersare used. Of course, the catalytic converter of the present inventionhas advantages over prior art catalytic converters. Because of theseadvantages, the catalytic converter can be used in ways in which knowncatalytic converters cannot be used.

Any of the specific embodiments of the substrate of the invention, asdescribed above, may be used in one or more of the specificapplications, e.g., catalytic converters. In a specific embodiment, thecatalytic converter comprises a catalytic substrate of the presentinvention; a matting surrounding said catalytic substrate; and acanister, preferably a metal canister; and optionally further comprisesa washcoat.

Another aspect of the present invention is directed to a catalyticconverter that is position in or adjacent to the exhaust manifold of anexhaust system of the engine, said converter comprising a catalyticsubstrate of the present invention. Such a catalytic converter isreferred to as a manifold catalytic converter (other terms includemani-cat, manifold converter, and the like). A mani-cat of the presentinvention includes mani-cats known in the art, wherein the catalyticsubstrate of the present invention is used in place of the prior artsubstrate. Such mani-cats are disclosed in, e.g., U.S. Pat. Nos.6,605,259; and 5,692,373.

In another embodiment, the invention is directed to an improvedcatalytic converter, the improvement comprising the novel substrate asdescribed herein. Any one of the specific embodiments of the substratecan be used in the improved catalytic converter.

In another embodiment, the invention is directed to an improvedcatalytic converter for treating internal combustion engine exhaustcomprising a substrate, a metal oxide washcoat, and at least onecatalyst adhered to the metal oxide particles, the improvementcomprising the substrate comprising a nSiRF-C composite and a catalyticmetal.

In another embodiment, the invention is directed to an improvedcatalytic converter for treating internal combustion engine exhaustcomprising a substrate, a metal oxide washcoat, and at least onecatalyst adhered to the metal oxide particles, the improvementcomprising the substrate comprising a nSiRF-C composite and a catalyticmetal.

In another embodiment, the invention is directed to an improvedcatalytic converter for treating internal combustion engine exhaustcomprising a substrate, a metal oxide washcoat, and at least onecatalyst adhered to the metal oxide particles, the improvementcomprising the substrate comprising an AETB composite

In another embodiment, the present invention is directed to a main-cathaving a catalytic substrate comprising a nSiRF-C composite and acatalyst. The main-cat (sometimes referred to as an underfloor catalyticconverter) is located partially or totally within the head of an engine.In one embodiment, the main-cat comprises a catalytic substrate of thepresent invention, wherein said substrate has a density of about 12lb/ft³, has a porosity of about 97%, has a low thermal expansion, has ahigh structural integrity, and has low heat conductance. In a preferredembodiment, the main-cat comprises about 600 cpsi and having a wallthickness of about 6 mils. The main-cat in this embodiment has awall-flow configuration. In a preferred embodiment, the main-cat has achannel shape of substantially box (varying lengths through thesubstrate) with substantially square openings (or holes). In a preferredembodiment, the catalytic substrate of the main-cat is made using thecomb method. Additionally, in this embodiment, the catalytic substratecomprises an alumina washcoat. In this embodiment, the main-cat iscapable of catalyzing both oxidation and reduction of pollutants, e.g.,it has a catalyst capable of oxidizing pollutants and it has a catalystcapable of reducing pollutants. The canister of the main-cat is preparedby a swagging method. In a preferred embodiment, the main-cat comprisestwo substrate units. The main-cat, in certain embodiments is used alone,or alternatively is used in combination with a pre-cat. In a preferredembodiment, the main-cat comprises an intumescent matting. The main-catcan be used in all internal combustion engines. The main-cat can be usedwith fuel-borne catalysts. Moreover, the substrate of the main cat maybe protection enhanced

The main catalytic converter of the present invention, as describedabove, is also used, in certain embodiments with one or moreaftertreatment systems. Such aftertreatment systems include an NOxadsorber, a HC adsorber, a SCR systems, and the like

Furthermore an embodiment having the same or similar configurations andattributes as the main catalytic converter described above can be usedfor a membrane catalyst. The membrane catalyst comprises a catalyticsubstrate having a membrane configuration as described above.

In another embodiment, the present invention is directed to a head-cathaving a catalytic substrate comprising a nSiRF-C composite and acatalyst. The head-cat is located partially or totally within the headof an engine. In one embodiment, the head-cat comprises a catalyticsubstrate of the present invention, wherein said substrate has a densityof about 12 lb/ft³, has a porosity of about 97%, has a low thermalexpansion, has high structural integrity, and has low heat conductance.In a preferred embodiment, the head-cat comprises about 600 cpsi andhaving a wall thickness of about 6 mils. The head-cat in this embodimenthas wall-flow configuration. In a preferred embodiment, the head-cat hasa channel shape of substantially pyramidal with substantially squareopenings (or holes). In a preferred embodiment, the catalytic substrateof the head-cat is made using the comb method. In this embodiment, thehead-cat is capable of catalyzing both oxidation and reduction ofpollutants, e.g., it has a catalyst capable of oxidizing pollutants andit has a catalyst capable of reducing pollutants. The head-cat, incertain embodiments is used alone, or alternatively is used incombination with a pre-cat. In a preferred embodiment, the head-catcomprises a hybrid matting. The head-cat can be used in all internalcombustion engines. The head-cat can be used with fuel-borne catalysts.

One or more head cats can be used with the same engine. The use of ahead cat in accordance with the present invention would also have one ormore of the following advantages: reduce weight of the under-floorexhaust system; increased filtration of exhaust particulate matter thatan intercooler would otherwise pick up, thereby improving the life ofinter-cooler; no matting is required; rattling sounds in heat shieldsreduced; reduced muffler size; enhanced burn-off of particulate matter;in case of a failure of one head cat, in certain embodiments, theexhaust gas would still be effectively treated with the otherfunctioning head cats, e.g., the other three on a 4-cylinder engine.Head-cats are advantageous for boats, watercraft, motorcycles, smallhandheld engines, leaf-blowers, and related engines, and in otherapplications in which a nonexposed catalytic converter is preferred.

In another embodiment, a catalytic converter of the present inventioncould be placed between the head and the exhaust manifold as shown inFIG. 41. In this embodiment, the catalytic converter section is placedbetween the engine head and the exhaust manifold. An advantage overconventional systems is that the converter is very close to thecombustion chamber, thus increasing efficiency. For instance, thisembodiment could put these on the Ford 4.6 liter and it would fit all oftheir engines. This in turn means that it would fit on the FordExplorer, Mustang, Crown Victoria, Econoline, 150/250/350 pickup,Expedition, and every other product that Ford puts the engine on, suchas Lincoln products. It would also fit in certain embodiments on thevarious model years that used it those many years. That one 4.6 castingwould be useful for millions of vehicles in the U.S. alone. It is alsofriendly for the oxygen sensors to go into as well.

In another embodiment, the present invention is directed to a back-cathaving a catalytic substrate comprising a nSiRF-C composite and acatalyst. In another embodiment, the catalytic converter of the presentinvention is a back-cat. The back-cat is located after the maincatalytic converter. In one embodiment, the back-cat comprises acatalytic substrate of the present invention, wherein said substrate hasa density of about 12 lb/ft³, has a porosity of about 97%, has a lowthermal expansion, has high structural integrity, and has low heatconductance. In a preferred embodiment, the back-cat comprises about 600cpsi and having a wall thickness of about 6 mils. The back-cat in thisembodiment has wall-flow configuration. In a preferred embodiment, thecatalytic substrate of the back-cat is made using the comb method. In apreferred embodiment, the back-cat has channel holes of varying shapes,including triangular, square, and hexagonal. Likewise the channel shapecan vary. In this embodiment, the back-cat is capable of catalyzing bothoxidation and reduction of pollutants, e.g., it has a catalyst capableof oxidizing pollutants and it has a catalyst capable of reducingpollutants. The back-cat, in certain embodiments is used alone, oralternatively is used in combination with a pre-cat. In a preferredembodiment, the back-cat comprises a non-intumescent matting. Theback-cat can be used in all internal combustion engines. In anotherembodiment, the back-cat is used in conjunction without fuel-bornecatalysts. Generally, the back-cat of the embodiment is place near thestandard muffler location, although other locations are possible. In analternative embodiment, the back-cat is integrated into a muffler. Suchan embodiment may comprise: a) the substrate itself acting as andreplacing a muffler, or b) the substrate is placed inside the typicalmetal muffler assembly so it is integrated into the muffler.

In another embodiment, the invention is directed to a diesel oxidationcatalyst (DOC), wherein the substrate of the DOC is a catalyticsubstrate as described herein. In a preferred embodiment, the substrateof the DOC of the invention is an AEBT or an OCBT, preferably AEBT-10,AEBT-12, AEBT-16, or OCBT-10. The embodiment of the DOC has a catalystselected from the group consisting of palladium, platinum, rhodium,mixtures thereof, and derivatives thereof.

Other suitable embodiments include a catalyzed DPF comprising acatalytic substrate of the present invention, preferably the substratecomprising an AETB material such as AEBT-12, and further comprising acatalyst.

Particulate Filter (DPF, DPT)

In another embodiment, the present invention is directed to aparticulate filter comprising a catalytic substrate of the presentinvention. The particulate filter of the present invention can be usedin an engine exhaust system in a similar manner in which known catalyticconverters are used. Of course, the particulate filter of the presentinvention has advantages over prior art catalytic converters. Because ofthese advantages, the catalytic converter can be used in ways in whichknown catalytic converters cannot be used.

In another embodiment, the invention is directed to an improvedparticulate filter, the improvement comprising the novel substrate asdescribed herein. Any one of the specific embodiments of the substratecan be used in the improved particulate filter.

In another embodiment, the invention is directed to an improvedparticulate filter for treating internal combustion engine exhaustcomprising a filtering substrate, the improvement comprising thesubstrate comprising a nSiRF-C composite having a plurality of channelsextending into and optionally through the substrate. The configurationof the channels can vary as provided for above.

In another embodiment, the invention is directed to an improvedparticulate filter for treating internal combustion engine exhaustcomprising a filtering substrate, the improvement comprising thesubstrate comprising a nSiRF-C composite having about 100 to about 1000,preferably about 600 channels extending partially through the substrate,and wherein said substrate has a wall-flow configuration.

In another embodiment, the invention is directed to an improvedparticulate filter for treating internal combustion engine exhaustcomprising a substrate, and a metal oxide washcoat, the improvementcomprising the substrate comprising AETB.

In another embodiment, the present invention is directed to a dieselparticulate filter (DPF) having a filtering substrate comprising anSiRF-C composite as described above. The filtering substrate isconfigured to be suitable for use in the DPF. The DPF is locatedpartially or totally within the head of an engine. In one embodiment,the DPF comprises a filtering substrate of the present invention,wherein said substrate has a density of about 12 lb/ft³, has a porosityof about 97%, has a low thermal expansion, has a high structuralintegrity, has low heat conductance. In a preferred embodiment, themain-cat comprises about 600 cpsi and having a wall thickness of about 6mils. The main-cat in this embodiment has wall-flow configuration. In apreferred embodiment, the main-cat has a channel shape of substantiallybox (varying lengths through the substrate) with substantially squareopenings (or holes). In a preferred embodiment, the catalytic substrateof the main-cat is made using the comb method. Additionally, in thisembodiment, the catalytic substrate comprises an alumina washcoat. Inthis embodiment, the main-cat is capable of catalyzing both oxidationand reduction of pollutants, e.g., it has a catalyst capable ofoxidizing pollutants and it has a catalyst capable of reducingpollutants. The canister of the main-cat is prepared by a swaggingmethod. In a preferred embodiment, the main-cat comprises two substrateunits. The main-cat, in certain embodiments is used alone, oralternatively is used in combination with a pre-cat. In a preferredembodiment, the main-cat comprises an intumescent matting. The main-catcan be used in all internal combustion engines. The main-cat can be usedwith fuel-borne catalysts. Moreover, the substrate of the main cat maybe protection enhanced. The protection coating may be applied to theinside or to the external surface of the substrate.

Canning Types

The catalytic converter of the present invention has a canister. Thecanister can be prepared according to known methods in the art.Furthermore, the canister of the catalytic converter or particulatefilter of the present invention may use materials known in the art,e.g., steel, to make the canister.

In a preferred embodiment, the catalytic converter of the presentinvention has an exit pipe that can be attached to a tailpipe ofcommercially available vehicles. Preferably, the catalyst converter fitstailpipes having a diameter of about 2½ or 3 inches.

For example, suitable canisters include those made according to any oneof the following methods: clamshell, tourniquet, shoebox, stuffing, andswaging. The above canning methods utilize two different gap controlmechanisms: (1) fixed gap and (2) fixed canning force. From the weldingprocess perspective, the methods produce converters with one or twoseams. These classifications are illustrated in Table 4 (Rajadurai1999).

Fixed Gap Fixed Force Single Seam Stuffing, Swaging Tourniquet Dual SeamClam Shell Shoebox

Closing the can using a fixed force offers a more accurate gap densitycontrol by eliminating the dimensional tolerance influence of thesubstrate, can, and the mat itself. Closing the can to a fixed gap hasthe advantage of producing a converter of fixed final dimensions, whichsimplifies the converter design, primarily in respect to welding ofcones to the finished can.

The single seam design is usually preferred for round or oval convertersof low aspect ratios, where it can provide uniform gap densitydistribution. Single seam shells also provide more manufacturingflexibility and require less expensive tooling. The dual seam design isusually required for oval converters with high aspect ratios. In thiscase, reinforcing ribs are stamped in the shell to prevent itsdeformation and the resulting gap nonuniformity. The dual seam shellsare produced in stamping processes which require very expensive toolingand have to be justified by high production volumes.

Clamshell

In one embodiment, the catalytic converter of the present inventioncomprises a canister made with the clamshell technique. In anotherembodiment, the particulate filter comprises a canister made with aclamshell technique. In North America, clamshell has been traditionallythe most common design of the underfloor converter in passenger cars andlight trucks. Construction of a clamshell catalytic converter isillustrated in FIG. 36. The ceramic catalyst substrate(s) is wrapped inthe mat and placed in the bottom part of the shell. Then, anothersymmetrical part of the shell is placed on the top, pressed together andwelded.

Tongue and groove design is used for the mounting mat to avoid bypassingof the substrate by exhaust gases. The converter illustrated above alsoincludes end seals. The seals are used here to protect the mat againstgas impingement and erosion, rather than to prevent leaks. Mostconverters which utilize mats do not have end seals. Whenever wire meshmount is used instead of the mat the end seals are required, at least atthe inlet face of the substrate.

Clamshell converters are often equipped with external heat shields.Internally insulated designs were also developed, with the inside ofclamshell stampings lined with an extra layer of thermal insulation.

Older designs of catalytic converters included support rings or deeppockets in the clamshell stampings to prevent axial movement of thesubstrate within the can. In a properly designed converter, whichutilizes intumescent mats of high holding pressures, such measures arenot required. There are many automotive converters without axial supportof the substrate, which still show an impressive durability record.However, the axial support may be required for larger and heaviersubstrates or when non-intumescent mats of lower holding pressure areused. Another consideration is the erosion of mat. The converter shellprofiles or end cones should be designed in such a way as to shelter themat from direct impingement of hot exhaust gases. Some convertermanufacturers impregnate mat edges, which are exposed to the gas, withchemicals to improve their erosion resistance. High holding pressures inmodern converters also improve the mat resistance to erosion.

Dual monolith converters are used in many automotive applications. Twoor more monoliths may be used due to monolith length manufacturingconstraints or to combine catalysts of different specifications in oneconverter. In most dual monolith converters the substrates are separatedby space, which is maintained by forming separate pockets in theclamshell stamping. In some designs, the space between substrates ismaintained by a metal or ceramic ring. A butted monolith position, withno space in between, is also possible. The butted design, which offersless pressure drop than the spaced design, has been used in somecommercial converters for gasoline engines (Kuisell, R. C., 1996,“Butting Monoliths in Catalytic Converters,” SAE 960555).

The converter shell geometry has to provide the required matcompression. The clamshell profiles include stamped reinforcing ribs inorder to provide the necessary stiffness and uniform pressuredistribution. This is especially important for flat oval catalystsubstrates. Care should be taken while designing the ribs that noexcessive pressure areas exist which could cause damage to the substrateor the mat. The clamshell method puts high requirements on thedimensional tolerances of the monoliths, as well as the clamshellstampings. The mat compression during clamshell canning proceeds untilthe half-shells close, producing a certain gap thickness. The gapthickness is determined by the dimensions of the monolith and of theshell. Therefore, any variations in the size of monoliths result invariations in the mat density and, consequently, in the canning pressurethat may cause converter durability problems.

Tourniquet is the most common method which allows direct control of themounting pressure during canning process. Since tourniquet isinsensitive to dimensional differences which may occur among thesubstrate monoliths, it is capable of producing the most robustcatalytic converters. In practice, the tourniquet method is limited toround or close-to-round catalyst substrate cross-sections. Itssuitability to oval or flat-oval automotive converters that are used inthe underfloor position is very limited. Tourniquet was once morepopular among car makers in Europe, but it became more common in NorthAmerica as automotive converters migrated from the underfloor locationto the engine close-coupled position. Tourniquet is also suitable forlarge diameter catalytic converters for heavy-duty diesel engines. Atourniquet catalytic converter is shown in

In the tourniquet technique the substrate is first wrapped in atongue-and-groove shaped mat. Then, the wrapped monolith is placedinside a longitudinally split can. The can is fabricated by rolling arectangular piece of sheet metal. The part of the rectangle which goesunderneath the overlap is usually tapered. In some designs theoverlapping part of the can is formed, through an additional stampingoperation, into a protruding lip to provide space for the can edgeunderneath the overlap. Such design prevents the inside edge of the canfrom cutting into the mat or creating a local pressure buildup which maydamage the canned part, especially when thin mats are used. Next, thecan with the wrapped monolith is placed in the tourniquet machine whichapplies a controlled force to the assembly. The can is tack welded whenstill under pressure, removed from the machine and seam welded. Apush-out test is sometimes carried out as a quality assurance measure.Axial monolith displacement caused by applying a controlled force ismeasured in a special test apparatus. Finally, the converter headers orend cones, as well as flanges and/or ports, are welded to the converterbody in a separate operation. The final assembly may be tested for weldquality by pressurizing with air while submerged in water.

The tourniquet machine includes a loop of a steel band that applies theforce to canned parts. One end of the loop is attached rigidly to themachine while the other is pulled by a pneumatic or hydraulic actuator.In some machines vibration is applied during canning to minimize theclosing force and to assure more uniform distribution of pressure.

The actual required canning force to achieve a target mount density fora given mat can be determined through a series of tests. Severalconverters should be closed using different closing forces. The canningforce that produced the desired mat density should be selected. Due tomat pressure relaxation, it is important that the tourniquet machineproduces repeatable closing speed and time patterns. After the targetclosing force is reached, the machine should maintain the can atconstant position, to allow for tack welding, rather than at constantforce. Applying constant force to the can as the mat pressure relaxeswould cause over-compression of the mat.

The shoebox technique utilizes a split, two part shell similar to theclamshell method. The shell, however, is closed under fixed force withthe edges of one of the half-shells overlapping those of the other.Therefore, the shoebox offers the robust packaging benefits oftourniquet in respect to its insensitivity to dimensional tolerances ofthe substrate.

Reinforcing ribs can be stamped on the shoebox shells. Thus, thistechnique allows for canning of flat-oval substrates in cases wheretourniquet would be inadequate.

Stuffing

In the stuffing technique, the mat wrapped monolith is pushed into acylindrical can. The can is usually made of a section of tube but it canalso be rolled of sheet metal and welded. Non-cylindrical shapes (e.g.,trapezoidal) are also possible. This method is applicable to both smallsized passenger car converters and large converters for heavy dutyengines. A stuffing cone is used to facilitate smooth insertion of themonolith (Li, F. Z., 2000, “The Assembly Deformation and Pressure ofStuffed Catalytic Converter Accounting for the Hysteresis Behavior ofPressure vs. Density Curve of the Intumescent Mat”, SAE 2000-01-0223),as shown in the figure. After completing the operation, the end conesare welded to each end of the cylinder to complete the can assembly.

Although stuffed converters have similar appearance to the tourniquetassemblies, the actual mechanism of substrate holding is the same as inthe clamshell design. In particular, the mat mounting pressure isdetermined by geometrical dimensions of the shell and of the monolith.As a consequence, high repeatability of substrate diameters is requiredwhen stuffing technique is used.

A modification of the stuffing technique—termed SoftMount Technology—hasbeen proposed by Corning (Eisenstock, G., et al., 2002, “Evaluation ofSoftMount Technology for Use in Packaging Ultra Thinwall CeramicSubstrates”, SAE 2002-01-1097). The objective was to minimize the peakmat pressure during stuffing to allow for canning of ultra-thin wallsubstrates characterized by lower strength. The key idea is to employ atapered cylindrical tool called an arbor, positioned ahead of thesubstrate, to take the peak pressure response of the mat duringinsertion.

In the SoftMount method, the mat is first inserted into the can where itis held on a flange during the process. Then, the mat-lined can ispushed down over the arbor and the substrate (i.e., the arbor ispositioned on the substrate). The arbor is chamfered inward at the endto slip easily into the can-mat assembly. The arbor compresses the matagainst the can as it moves through. As the substrate moves intoposition replacing the arbor in the can, it is not exposed to theinstantaneous peak loads required to compress the mat.

Swaging

In swaged converters, the converter shell is machined down to thedesired diameter after the mat-wrapped substrate has been inserted.Swaging is a newer packaging technique, performed in fully automated,CNC-controlled equipment suitable for high volume production forpassenger car applications. Swaged converters can be manufactured fromone section of tube together with their end cones, which are obtained ina spin forming process in the same production machine.

The gap control mechanism can be classified as constant gap thickness,as it is the case with stuffing, but CNC-controlled production lines canautomatically account for differences in the substrate diameter. Swagedconverters must be initially formed to diameters slightly less than thetarget diameter of finished product, to allow the shell to “spring back”after machining. This is a disadvantage of this method, which may leadto excessive peak pressures and substrate damage during canning.

Catalytic converter headers provide the transition between the inlet andoutlet pipes and the substrate cross-section. Most converter headers areshaped as cones or funnels with axial gas flow. Other designs, such astruncated headers (Wendland, D. W., et al., 1992, “Effect of HeaderTruncation on Monolith Converter Emission Control Performance”, SAE922340) or headers with tangential gas inlet are possible but uncommon.The function of the inlet header is to diffuse the inlet flow, i.e., todecrease the gas velocity and increase its static pressure with aslittle loss in total pressure as possible. In practice, combined headerlosses can constitute from 10% to 50% of the overall converter pressuredrop, depending on geometry and flow conditions. These pressure lossescan be minimized by designing converter inlet headers which wouldprovide more uniform flow distribution. There is also a notion thatuniform flow distribution in a catalytic converter improves its emissionperformance and/or durability. In one embodiment of the presentinvention, the catalytic converter or particulate filter has a headerhaving an angle of about 30%.

Matting

A catalytic converter or particulate filter of the present inventionalso optionally comprises a matting. Any of the embodiments recitedabove or below may comprise a matting. In certain embodiments, thepresent invention further comprises a mat (or matting or batting). Forexample, a catalytic converter of the present invention, in anembodiment, comprises a catalytic substrate as described above, a mat,and a canister. Mats useful for use in the present invention are knownin the art.

A mat in certain embodiments can be selected based on a number ofattributes as described herein and known in the art. The catalyticconverter canister is preferably designed in such a way as to providethe required mounting pressure for a given catalytic substrate and agiven mat. The mounting pressure of the mat increases exponentiallyduring the compression from its initial bulk density to the final targetdensity. The mounting pressure exhibits viscoelastic relaxation, i.e.,the peak initial pressure that occurs at the canning decreasessignificantly during the first seconds or minutes thereafter due to therealignment of mat fibers (Myers 2000). The mounting pressure loss ofintumescent mats due to the relaxation varies between 30 and 60% of theinitial peak mounting pressure.

Due to the mat relaxation, as well as later in-service pressure losses,the mounting pressure is not a convenient parameter for the canningprocess specification. Instead, the mounting density—often called thegap bulk density (GBD)—is commonly used for that purpose. Typical matmounting densities along with their bulk (uncompressed) densities, arelisted in Table 2. The exact density for a given application should beconsulted with the mat manufacturer. The exact density for a givenapplication should be consulted with the mat manufacturer. called basisweight. The weight/area is expressed in g/m² or kg/m² (since these areunits of mass rather than weight, the customary term “weight/area”should be, strictly speaking, replaced by “mass/area”). Available matshave their weight/area in the range from 1050 to 6200 g/m² anduncompressed thickness between 1.5 and 10 mm. Intumescent mats of3000-4000 g/m² are typically used for automotive converters. Higher matweights, such as 6200 g/m² (6.2 kg/m²), are recommended for moredemanding applications or for large converters.

Another important property of catalytic converter mounting mats is theirweight/area ratio, sometimes also called basis weight. The weight/areais expressed in g/m² or kg/m² (since these are units of mass rather thanweight, the customary term “weight/area” should be, strictly speaking,replaced by “mass/area”). Available mats have their weight/area in therange from 1050 to 6200 g/m² and uncompressed thickness between 1.5 and10 mm. Intumescent mats of 3000-4000 g/m² are typically used forautomotive converters. Higher mat weights, such as 6200 g/m² (6.2kg/m²), are recommended for more demanding applications or for largeconverters.

Packaging mats can undergo erosion caused by the impingement of hotexhaust gases. Resistance to erosion is an important characteristic ofthe mat. The resistance to erosion depends strongly on gap bulk density.(Rajadurai, S., et al., 1999. “Single Seam Stuffed Converter Design forThinwall Substrates”, SAE 1999-01-3628).

Many other attributes of the mounting mats are specified and/or testedand are available from mat manufacturers. The list of these attributesincludes thermal conductivity, gas sealing attributes, frictioncoefficients, and more.

During the design of a mounting system, the following considerations, incertain embodiments, are accounted for:

Mounting Pressure: Assuming that the mounting mat is the sole means ofconnecting the substrate to the shell (i.e., the converter has no endseals or support rings), the mechanical connection is provided by theradial pressure in combination with friction at the mat surface.Mounting pressure is the minimum pressure required to hold the substratein place.

Peak Mounting Pressure. As mentioned earlier, mats behave likeviscoelastic solids, producing high peak mounting pressures duringinitial compression, followed by a gradual relaxation to reach theresidual mounting pressure. In thin wall substrates, the peak pressuresmay cause damage to the catalyst core during packaging. The transientbehavior of mats has to be also considered when designing canningmethods that rely on constant force, as opposed to constant gap size,such as tourniquet.

Temperature Behavior. For intumescent mats, the mat pressure dependsupon achieving sufficient temperature to activate the vermiculite. Aninlet temperature of at least 500° C. is required for vermiculiteactivation; higher inlet temperatures may be needed, depending on heattransfer conditions in the particular system. In gasoline applications,the mat is activated on the vehicle during the initial hours of engineoperation. Oven-treatment of catalytic converters may be required indiesel applications, where the exhaust gas temperature may never reachsufficient levels during regular vehicle operation. Vermiculiteexpansion is in part reversible, causing the mat to expand astemperatures increase and contract when the converter is cooled down.This property of vermiculite more than compensates for the expansion ofconverter shell, producing very high mounting pressures at highertemperatures. In contrast, non-intumescent mats show approximatelyconstant mounting pressure across the temperature range. The slightdecrease of the pressure with increasing temperature visible in FIG. 4can be attributed to gap expansion due to the thermal expansion of theconverter shell. At temperatures above 500° C., intumescent mats providehigher holding pressures than non-intumescent mats. However, attemperatures below 500° C., the mounting pressure from intumescent matsis actually much less than that from non-intumescent mat. Therefore,non-intumescent mats are the preferred mounting material in many dieselapplications where the converter inlet temperature remains below 500° C.Intumescent mats of reduced vermiculite content produce mountingpressures between the conventional intumescent mats and non-intumescentmats. Hybrid mats show pressure levels similar to non-intumescent mats,but they maintain a certain pressure boost at high temperature, whichcounteracts the gap expansion.

Gap Expansion. When the converter is exposed to high temperature, thegap thickness increases due to the differences in thermal expansioncoefficients between the substrate and the shell. The thermal expansionof the gap can be a significant source of mounting pressure loss. Thegap expansion is especially critical in applications wherenon-intumescent mats are used, as it cannot be compensated byvermiculite expansion. As a design guideline, the gap expansion shouldbe kept below 10% (Olson, J. R., 2004, “Diesel Emission ControlDevices—Design Factors Affecting Mounting Mat Selection,” SAE2004-01-1420).

Gap expansion depends on the following design factors:

Substrate diameter: larger substrates result in higher percentage gapexpansion. Therefore, gap expansion can be still a problem in heavy-dutydiesel applications, despite the relatively low converter temperature.

Gap thickness: thicker gaps result in less gap expansion.

Shell temperature: higher temperatures produce more gap expansion.

Shell material CTE: steels of higher thermal expansion coefficientsproduce higher gap expansion. Therefore, the gap expansion is easier tocontrol using ferritic (as opposed to austenitic) steel grades.

Mat Aging. Once the converter is put in service, the intumescent matexpands, causing an increase of mounting pressure. A number of otheraging factors are responsible for gradual irreversible loss of mountingpressure, as follows: thermal cycling; vibration acceleration and othermechanical factors; soaking of the mat by water (condensate, vehiclewashing); and organic binder burn-out when the mat is first heated.

Advantages and Disadvantages of Current Mats

Conventional applications utilize intumescent and non-intumescentfibrous mats for mounting a honeycomb substrate in canisters, asexemplified in European Patent Application No. EP0884459 to Locker andEuropean Patent Specification No. EP0912820 to Hwang. In accordance withone conventional system, the fibrous mat only allows for mounting alarger catalyst member in a canister.

Intumescent Mats

Intumescent mats were originally developed for gasoline converters. Bythe early 1990's, they became the most common type of ceramic mat usedin catalytic converters for all internal combustion engine applications,including diesel. Intumescent mats have the property of partlyirreversible expansion once exposed to high temperatures. Thermalexpansion curves for the mats are available from several manufacturersincluding 3M and Unifrax. Once expanded, they increase the holdingpressure on the substrate providing a very secure mounting system.Because of their temperature expansion characteristics, intumescent matscan actually increase their mounting pressures at high temperatures,compensating for the mounting pressure loss due to the thermal expansionof the steel housing.

Intumescent mats are made of alumina-silica ceramic fibers and containvermiculite, which provides their thermal expansion. Typicalcompositions have 30-50% of alumina-silica fibers, 40-60% ofvermiculite, and 4-9% of an organic binder (typically acrylic latex).After the converter is assembled, the mat has to be exposed totemperatures on the order of about 500° C. to achieve the initialexpansion, which is usually achieved on the vehicle during the initialhours of engine operation. The organic mat binder, which decomposes athigh temperatures, is responsible for the characteristic odor emittedwhen the mat is first heated.

The vermiculite component imposes relatively low maximum operatingtemperature limits for intumescent mats. The mats lose their holdingpressure dramatically at temperatures of about 750° C. That temperatureis usually defined as the average mat temperature. Therefore, mats canbe used at higher exhaust temperatures provided there is a temperaturegradient across the mat due to heat losses from the outside convertershell. The use of intumescent mats is limited in hot isothermalapplications where no heat loss occurs through the converter wall. Suchsituations include catalysts mounted inside mufflers, e.g., formotorcycle applications.

High content of the vermiculite component is also responsible for highmounting pressures, especially at higher exhaust temperatures. Thepressure from intumescent mats was found to be excessive for ultra-thinwall substrates, resulting in possible damage to the parts. For theseapplications, mat manufacturers introduced reduced vermiculiteintumescent mats (sometimes referred to as “advanced” or “2ndgeneration” intumescent mats), which provide less mounting pressure thanthe conventional design.

Non-Intumescent Mats

Non-intumescent mats do not contain vermiculite. Therefore, they canprovide much higher temperature limits of about 1250° C. The maincomponent of non-intumescent mats is alumina fiber, with addition oforganic binders. In certain embodiments of the present invention, thecatalytic converter or particulate filter comprises a substrate asdescribed herein and a non-intumescent mats may be better with fibrousmaterials.

The substrate support relies on built-in compression or fiber “spring,”which supplies constant holding pressure across the applicationtemperature range. Since the converter shell expands with temperature, adecrease of the effective converter mounting pressure is observed athigher temperatures. Therefore, the non-intumescent mats, quite oppositeto vermiculite mats, hold the catalyst substrate most securely at lowtemperatures. As the temperature increases, the substrate inside theconverter is held with decreasing force.

Non-intumescent mats can be used not only in high temperatureapplications which cannot withstand high mounting pressures (thin wallsubstrates), but also in low temperature converters, such as those fordiesel engines. Since they are not dependant on the vermiculiteexpansion, they do not require oven treatment in low temperature dieselconverters.

Hybrid Mats

An improved catalytic converter or particulate filter of the presentinvention may further comprise a hybrid mat. Such mats are known in theart. A hybrid mat, in one embodiment, incorporate a two-layered design:a layer of intumescent mat on top of a layer of non-intumescent mat.Their attributes and performance are also in-between, with better lowtemperature mounting pressure than intumescent mats, but higher hightemperature pressure than non-intumescent mats. In a preferredembodiment, the improved diesel particulate filter of the presentinvention comprises a hybrid mat, for use in both light- and heavy-dutyapplications.

Wire Mesh

Knitted stainless steel wire mesh may be used instead of mats to packageceramic catalyst substrates. Wire mesh is often considered to exhibitless favorable mounting pressure characteristics than mats, but is stillused in some catalytic converters (traditionally, wire mesh had beenused by Ford). End seals are always required with wire mesh to preventbypassing of the substrate by gas.

Auxiliary Heating Source

As another configuration or exemplary embodiment to those previouslydisclosed, the filter element could include the addition of a series ofelectric heating rods added to the substrate after the catalyst isapplied. Preferably, the heating elements are applied after the catalystto prevent the curing process from harming any electrical contacts. Inone embodiment, the heating elements or rods are placed approximately ¼inch apart from each edge or any distance that is desired. In certainembodiments, one could also use a wire mesh configuration, or otherheating element described herein, that is placed perpendicular to thegas flow direction and installed during the formation of the fiberblank. The electrical contacts could be protected with Nextel fabric ora similar material. The heating elements could be activated before anengine starts as a prewarmer and will remain in operation, eitherpartially or in full operation, until the exhaust temperature exceed thetemperatures achieved by auxiliary heating elements.

The use of auxiliary heating source applied to the filter foundation maybe useful to increase the temperature inside of the filter foundationand/or to evenly distribute additional heat throughout the filterfoundation making it more efficient. The auxiliary heat source may becomprised of resistant electric heating elements. The heating elementsmay have a rod configuration which can be inserted after filterfoundation formation or during the sol-gel process. The filterfoundation can have one or more electric heating elements applied andthe heating elements can be heated simultaneously, independently, and ina cycled, patterned, or random series. The heating elements could be inthe form of a wire mesh configuration which can be inserted during orafter the filter foundation formation. The filter can employ the use ofa single wire mesh or a plurality of wire mesh heating elements andthose heating elements can be heated simultaneously or individually.Additionally, the mesh heating elements can be heated in a cycled,patterned or random series. The heating elements may also utilize rods,spirals or helical configurations inserted during or after formation.The filter foundation may incorporate one or more spiral or helicalheating elements which may be heated simultaneously or independentlyincluding the use of a cycled, patterned or random series. Finally, thefilter foundation may incorporate a combination of any of the heatingelements previously described.

In addition to the resistant electrical heating elements described abovethe auxiliary heat source may also use infra-red or microwave heatheating elements. The various heat sources may be implemented inside ofthe filter foundation itself or may be employed to heat the filterfoundation as an exterior heating element. Once again, various heatsources may be applied independently or in combination with any of theother heating elements or sources.

The filter foundation will be encased in a casing with sufficientdurability to protect the filter foundation from normal impactsencountered with vehicle transportation. Such a casing may include acommon metal casing such as stainless steel, steel or another metalalloy. The material may also be non-metallic including ceramic-basedcasings. The filter foundation may be encapsulated in insulation orbatting prior to being enclosed in the casing. The present invention mayalso incorporate a heat shield.

The entry and exit tubes of the filter foundation may be coated with anoxidation catalyst. The catalyst may make the radiation process quickerwhich results in the system as a whole treating the exhaust in a muchfaster time. The catalysts may be a noble metal catalysts includingthose which are platinum, palladium, or are rhodium based, as well asothers. The catalyst may be applied directly to the filter foundationsurface. Application of the catalyst may be sprayed on, applied bydipping the filter foundation into a solution or injected into thefilter foundation itself. The use of an oxidation catalyst will promotethe ignition of the particulate matter at a lower temperature. Inaddition, a catalyst can also be used as a supplemental heater withinthe filter foundation itself.

The exhaust filter system can be integrated with the engine exhaust pathincluding integration inside the exhaust manifold of the engine itself.Because the filter foundation is so durable to heat and vibration it canbe placed immediately next to an engine exhaust as it exits the engineblock. The unique ability of the filter foundation to withstand highheat and increased vibrational stress allows the placement of thepresent invention much closer to the engine. The close placementprovides advantage over conventional exhaust filters or catalyticconverters which cannot withstand such high heat or vibrational stress.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to those skilled inthe art that various changes and modifications can be made thereinwithout departing from the spirit and scope thereof. Thus, it isintended that the present invention cover the modifications andvariations of this invention provided they come within the scope of theappended claims and their equivalents.

Specific Embodiments of a Catalytic Converter

The catalytic converter and particulate filter of the present inventionare further illustrated by the following nonlimiting specificembodiments. A number of specific embodiments recited herein exemplifybut do not necessarily limit the scope of the invention. A catalyticconverter of the present invention can be used on any number of enginesand vehicles. Thus, in one embodiment, a catalytic converter of thepresent invention is suitable for use on a vehicle or engine produce byany one of the following companies: Daimler-Chrysler; Chrysler; Dodge;Eagle; Jeep; Plymouth; General Motors; AM General (e.g., HUMMERs);Buick; Cadillac; Chevrolet; Geo; GMC; Hummer; LaSalle; Oldsmobile;Pontiac; Saturn; Ford; Continental; Lincoln; Mercury; Ace Motor Corp;American Motors; Avanti BMW; Daimler-Chrysler; Fiat; Ford; GAZ; GeneralMotors; Honda; Mitsubishi; Renault; Peugeot; Toyota; and VolkswagenGroup. Others include Holden; Lightburn; Hartnett; Alpha Sports; Finch;Amuza; Australian Kitcar; FPV; Bavariacars; Birchfield; G-Force; Bomac;Bullet; Homebush; Carbontech; HSV; Classic Glass; Kraftwerkz; ClassicRevival; Cobra Craft; Piper; Daktari; PRB; Daytona; Python; DeuceCustoms; RCM; Devaux; RMC; DRB; Roaring Forties; Elfin; Robnell; Evans;Austro-Daimler; OAF; Puch; Steyr; Steyr-Daimler-Puch; FN; Germain;Miesse; Minerva; Nagant; Vivinus; Gurgel; Puma; A-E; AC; Allard; Alvis;Ariel; Armstrong Siddeley; Ashley; Aston Martin; Austin; Austin-Healey;Bentley; Berkeley; Bond; Bristol; BSA; Caterham; Clan; Daimler; Dellow;De Lorean; Elva; F-L; Fairthorpe; Ford; Frazer Nash; Gilbern; Ginetta;Gordon-Keeble; Hillman; Humber; Jaguar; James and Browne; Jensen;Jowett; Lagonda; Lanchester; Land Rover; Lea-Francis; Lister; Locost;Lotus; M-R; Marcos; McLaren; MG; Morgan; Morris; Mini; Ogle; Panther;Peerless/Warwick; Piper; Range Rover; Reliant; Riley; Rochdale;Rolls-Royce; Rover; S-W; Singer; Standard; Sterling; Sunbeam; Swallow;Talbot; Tornado; Trident; Triumph; Turner; TVR; Vanden Plas; Vauxhall;Wolseley; Bricklin; McLaughlin; Aero; Jawa; Laurin & Klement; Praga;Skoda; Tatra; Walter; Kewet; Elcat; Valmet; RaceAbout; Amilcar; Alpine,aka. Alpine-Renault; Bonnet; Bugatti; CD; CG; Citroën; DB; DeDion-Bouton; Delage; Delahaye; Delaunay-Belleville; Facel Vega; Gordini;Hispano-Suiza; Hotchkiss; Peugeot; Renault; Rosengart; Simca;Sizaire-Naudin; Talbot; Tracta; Venturi; Voisin; A-G; Amphicar; Audi;Auto-Union; BMW; Fendt; Glas; Goggomobil; H-P; Heinkel (Heinkel Trojan);Horch; Käsbohrer-Setra; Kleinschnittger; MAN; Magirus; Maybach;Mercedes-Benz; Merkur; Messerschmitt; Neoplan; NSU; Opel; Porsche; S-W;Smart; Stoewer; Titan; Trabant; Volkswagen (VW); Wartburg; Wanderer;Thomond; Bajaj Tempo; Hindustan; Mahindra; Maruti; Premier; Reva; SanStorm; Sipani; Tata; Abarth; Alfa Romeo; Autobianchi; Bugatti AutomobiliSpA; De Tomaso; Dino; Ferrari; Fiat; Iso; Innocenti; Isotta Fraschini;Itala; Lamborghini; Lancia; Maserati; OM; Piaggio; Qvale; Vespa; Zust;Daihatsu; Honda (also Acura); Isuzu; Mazda; Mitsubishi; Mitsuoka; Nissanaka. Datsun (also Infiniti); Subaru; Suzuki; Toyota (also Lexus);Proton; ACE; AMI; AMM; Bufori; Inokom; Naza; Perodua; Swedish Assembly;Tan Chong; TD 2000; Donkervoort; Spyker; DAF; Pyonghwa; Tokchon; Kewet;Think aka. Pivco; Troll; Syrena; UMM; Aro; Dacia; Marta; Oltcit; Volga;Moskvitch; GM Daewoo Motors; Hyundai Motor Company; Kia Motors; RenaultSamsung Motors; SsangYong Motor Company; Nilsson; Nordic Uhr; S.A.M.;Saab; Scania; Thulin; Tidaholm; Tjorven (sold as Kalmar on the exportmarket); Volvo; and Yugo.

Catalytic or Filtering Muffler

In another embodiment, the present invention is also directed to acatalytic muffler comprising a catalytic or filtering substrate of thepresent invention. As described herein, the catalytic substrate orfiltering substrate is housed together with a muffler in a singlecannister.

In one embodiment, the catalytic muffler of the present comprises acatalytic muffler of known design in which the prior art catalyticsubstrate is replaced with the catalytic substrate of the presentinvention. Suitable known catalytic mufflers include those disclosed inU.S. Pat. Nos. 6,622,482; 6,604,604; 6,341,662; and 4,457,895.

Exhaust Systems

In another embodiment, the present invention is directed to an exhaustsystem comprising a catalytic substrate of the present invention. Anexhaust system generally comprises a number of components. The exhaustsystem comprises an engine and a suitable means for directing exhaustgas away from the engine.

The exhaust system comprises an internal combustion engine and a conduitfor directing the exhaust gas away from the exhaust ports of thecombustion chamber. Other optional components of an exhaust systeminclude an exhaust manifold, a muffler, and an exhaust pipe.

In another embodiment, the present invention is directed to an exhaustsystem comprising a filtering substrate of the present invention.

In another aspect, the present invention is directed to an improvedexhaust system utilizing a catalytic substrate of the present invention.In another aspect, the present invention is directed to an improvedexhaust system utilizing a filtering substrate of the present invention.

The exhaust system of the present invention is suitable for use with anyone of the following: 1) Mobile On-Road Engines, Equipment, andVehicles, including cars and light trucks; highway and streetmotorcycles; heavy-duty highway engines, such as trucks and buses; 2)Mobile Non-Road Engines, Equipment, and Vehicles, includingcompression-ignition engines (farm, construction, mining, etc.); smallspark-ignition engines (lawn mowers, leaf blowers, chainsaws, etc.);large spark-ignition engines (forklifts, generators, etc.); marinediesel engines (commercial ships, recreational diesel, etc.); marinespark-ignition engines (boats, personal watercraft, etc.); recreationalvehicles (snowmobiles, dirt bikes, all-terrain vehicles, etc.);locomotives; aviation (aircraft, ground support equipment, etc.); and 3)Stationary Sources, including hundreds of sources, such as power plants,refineries, and manufacturing facilities. In another embodiment, theinvention is directed to an exhaust system comprising a substrate,catalytic converter, particulate filter, or catalytic muffler of thepresent invention.

Other suitable exhaust systems of the present invention include thoseused in certain marine vehicles. The catalyst is typically positioned inan exhaust pipe leading from the engine. This exhaust pipe that leadsthrough a chamber in the hull of the craft to an outlet near the stern.This arrangement causes the exhaust pipe to be susceptible to vibration,especially with prior art substrates. In addition, in personalwatercraft the amount of space in which the engine may be positioned islimited so as to maintain the craft small in dimension and with a lowcenter of gravity. Moreover, certain prior art substrates such ascordierite should not be placed too close to the engine (overheating andmelting is possible). A marine vehicle exhaust system comprising acatalytic converter or particulate filter of the present invention mayovercome one or more of these problems. The catalytic converter orparticulate filter may be positioned in the marine exhaust system at thesame place the traditional converter or filter is positioned, or it maybe placed in another position. For example, in certain embodiments, thecatalytic converter is smaller than a prior art catalytic converter buthas substantially the same efficiency in removing and/or filteringpollutants. See for example U.S. Pat. No. 5,983,631 (Yamaha HatsudokiKabushiki Kaisha).

In other embodiments, the exhaust system of the present inventioncomprises one or more additional aftertreatment devices or methods thatare used to reduce or limit the pollutants that are emitted from anexhaust system. Suitable devices and methods include CRT, EGR, SCR,ACERT, and the like. For example, in one embodiment, the exhaust systemcomprises a catalytic converter of the present invention and a CRT. Theexhaust system may further comprise an SCR system. Additionalcombinations and variations are possible and are understood to be withinthe scope of the invention.

In another embodiment, the present invention is directed to an exhaustsystem comprising a NOx adsorber having a catalytic substrate comprisinga nSiRF-C composite and a catalyst. The main-cat is located partially ortotally within the head of an engine. In one embodiment, the main-catcomprises a catalytic substrate of the present invention, wherein saidsubstrate has a density of about 12 lb/ft³, has a porosity of about 97%,has a low thermal expansion, has a high structural integrity, has lowheat conductance. In a preferred embodiment, the main-cat comprisesabout 600 cpsi and having a wall thickness of about 6 miles. Themain-cat in this embodiment has wall-flow configuration. In a preferredembodiment, the main-cat has a channel. In a preferred embodiment, thechannels of the catalytic substrate of the main-cat are made using thecomb method. Additionally, in this embodiment, the catalytic substratecomprises an optional washcoat. In this embodiment, the main-cat iscapable of catalyzing both oxidation and reduction of pollutants, e.g.,it has a catalyst capable of oxidizing pollutants and it has a catalystcapable of reducing pollutants. In a preferred embodiment, the NOxcombination exhaust system comprises an intumescent matting. Themain-cat can be used in all internal combustion engines. The NOxcombination system is preferably used without fuel-borne catalysts.Generally, the NOx combination exhaust system has the substrate locatednear the muffler, although other locations are possible.

Vehicles

In another embodiment, the present invention is directed to an improvedvehicle, said improvement comprising a catalytic converter or aparticulate filter according to the present invention. The improvedvehicle includes in various embodiments, any of the specific embodimentsof catalytic converters and particulate filters described herein.

Suitable exemplary improved vehicles include vehicles made by one ormore of the following companies: Daimler-Chrysler; Chrysler; Dodge;Eagle; Jeep; Plymouth; General Motors; AM General (e.g., HUMMERs);Buick; Cadillac; Chevrolet; Geo; GMC; Hummer; LaSalle; Oldsmobile;Pontiac; Saturn; Ford; Continental; Lincoln; Mercury; Ace Motor Corp;American Motors; Avanti BMW; Daimler-Chrysler; Fiat; Ford; GAZ; GeneralMotors; Honda; Mitsubishi; Renault; Peugeot; Toyota; Volkswagen Group;and Yugo.

EXAMPLES Example 1

Residence time, or burn off time, is the amount of time for hydrocarbonsfrom the exhaust emissions to abide within the emission filter tocomplete combustion or oxidation. The residence time of the presentinvention is significantly better than conventional systems. FIG. 19provides a graph of the residence times 1902, 1904, 1906, 1908 requiredto combust or burn soot at temperatures 600 Kelvin, 900 Kelvin, 1000Kelvin, and 1200 Kelvin, respectively. The more kinetic energy possessedby particles, the higher likelihood of a successful reaction. As shownin FIG. 19, the residence time 1902 to combust or burn soot having 0.9soot mass at 600 degrees Kelvin is much longer than the residence time1908 at 1200 degrees Kelvin. The longer the residence time, the smallerthe allowable through-put volumes and the greater the risk of moreparticulate accumulating on and clogging the filter pores. Clogging canalso be a result of the ceramic material overheating to the point ofmelting, thereby blocking or clogging the pores. Residence time values1902, 1904, 1906 are indicative of cordierite samples. Residence times1902, 1904, 1906 range from about two minutes to twenty hours tocomplete combustion.

Example 2 Substrates

Substrates 1-7 were prepared as described herein. AETB-12 was purchasedfrom COI Ceramics and used as the nSiRF-C material of choice with adensity of 12 lbs/ft³. The substrate/filter was machined from AETB-12billets measuring 8×8×4 using standard carbide drill bits tippedmachining methods described in this patent. The substrate was machinedin a cylindrical shape with the following dimensions: radius of 2inches, longitudinal length of 1 inch.

Flow-through, wall-flow and mixed flow-through/wall-flow channels weredrilled into the substrate using standard CNC drilling methods describedin this patent and known in the art. A 0.042″ diameter stainless steeldrill bit was used at 10,000 RPM to drill the channels. During thedrilling process, it was observed that due to the high thermalemissivity and conductivity of the material, the drill bit was exposedto high temperature environments that led to damage and eventual meltingof the drill-bits. Wall thickness was not measured.

Substrates 1 and 2 had a flow through configuration. Substrates 3-6 hada wall flow configuration. Substrate 3 had about 25% of the channels asflow through and about 75% as wall flow. Substrate 4 had about 50% ofthe channels as flow through and about 50% as wall flow. Substrate 5 and6 had about 75% of the channels as flow through and about 25% as wallflow.

Some of the substrates were coated with an alumina washcoat, followed bya 5:1 Pt:Rh ratio catalyst coating. Specifically, Substrates 1, 2, and 7were not coated with any chemical. Substrates 3, 4, 5, and 6 were givena uniform washcoating utilizing standard techniques known in the priorart. The mass of washcoat applied to each substrate is given in thecolumn titled Mass of Washcoat. Following the washcoating, a catalystmixture comprising 5:1 Pt/Rh was applied to the substrates 3, 4, 5, and6 using standard methods. The mass of catalyst mixture applied to eachsubstrate/filter is given in the column titled Mass of Catalyst (g/ft³).The substrates with washcoat and precious metal catalyst loadings werecanned using techniques known in the prior art.

Weight of Estimated H2O ABS. Dry amount of Mass of WET Mass of SubstrateSubstrate WET washcoat washcoat Washcoat WT. H2O ABS Catalyst Number(grams) GMS NET g/in3 FIRED(g) (g/in3) (0) (g/in3) WET(g) (grams) 1 29.0178.5 149.4 2.91 63.0 2.71 — — 2 28.9 182.0 153.1 2.99 65.3 2.90 3 30.0158.0 128.0 2.50 61.0 2.50 167.4 8.47 164.9 24.3 Pt 4.8 Rh 4 30.4 163.3132.9 2.59 61.9 2.51 168.4 8.50 155.1 21.8 Pt 4.4 Rh 5 30.3 165.7 135.42.64 62.0 2.52 169.8 8.58 170.4 25.3 Pt 5.1 Rh 6 30.9 184.6 153.7 3.0067.3 2.90 202.5 31.6 Pt 6.3 Rh Ave = 8.52 Ave = 30.9 S/D = 0.23 S/D =5.0 N = 3 N = 4 7 24.3 105.1 80.8 2.47 44.6 2.54 99.7 20.2 Pt 4.0 Rh

Example 3 Preparation of Catalytic and Filtering Substrates

Substrates/Filters were prepared exactly as described in Example 2unless mentioned explicitly.

In a marked difference from the substrate/filters in Example 1, thefinal depth of ¾ inches into the 1 inch slug the comb assembly wasremoved from the CNC and the opposite (mirror image) comb assembly wasmounted onto the CNC punch and the same process for pecking method ofbroaching was employed. The end result this machining methodology is a600 cpsi with 6 mil walls and ½ inch wall flow overlap. As shown in FIG.28, the dimensions of the substrate/filter in wall-flow configurationwere 1″ diameter by 1″ thickness and the pattern inside that slug was0.8″ by 0.8″ square. This substrate was used to conduct an early-stagesuccessful Delta P-test to observe the drop in pressure observed in a N₂gas flow due to the obstruction in flow caused by wall-flowconfiguration. FIG. 29 demonstrates the drop in pressure measured in areactor-tube flow-measurement system as a function of gas flow rate fortemperatures of 27° C., 29° C. and 400° C. FIG. 30 demonstrates the dropin pressure measured in the same reactor as a function of temperature ata constant flow rate of 125 SLPM. These initial results were positiveand indicative that the nSiRF-C substrates/filters do not generate highback-pressure in the wall-flow configuration.

Example 4 Preparation of Catalytic and Filtering Substrates

Substrates/Filters were prepared exactly as described in Example 2unless mentioned explicitly.

In a marked difference from the substrates in Example 1, three differentsubstrates were generated using AETB-11, AETB-12, and AETB-16 billetspurchased from COI Ceramics with densities of 11, 12, and 16 lbs/ft³respectively.

For the substrate/filter created from AETB-11, the final depth of ¾inches into the 1 inch slug the comb assembly was removed from the CNCand the opposite (mirror image) comb assembly was mounted onto the CNCpunch and the same process for pecking method of broaching was employed.The end result this machining methodology is a 600 cpsi with 6 mil wallsand ½ inch wall flow overlap. For the substrates/filters created fromAETB-12 and AETB-16, the final depth of ⅞ inches into the 1 inch slugthe comb assembly was removed from the CNC and the opposite (mirrorimage) comb assembly was mounted onto the CNC punch and the same processfor pecking method of broaching was employed. The end result thismachining methodology is a 600 cpsi with 6 mil walls and ¾ inch wallflow overlap.

The dimensions of the all substrates/filters tested in this stage were1″ diameter by 1″ thickness. The substrates were exposed to anotherearly-stage Delta P-test to observe the drop in pressure observed forsubstrates material density and wall-flow configuration as a function ofspace hourly velocity. This particular test was conducted at 932Fahrenheit temperature. The results of our tests are summarized in FIG.31. In addition to the data observed for our AETB-11, AETB-12 andAETB-16 substrates/filters, the results reported by Corning for their400/6.6 flow-through cordierite substrates/filters and 200/12 cordieriteDPT (wall-flow configuration). Corning data was obtained through CorningTechnical Reports. Our results indicate that while Corning DPT in wallflow configuration causes excessive backpressure compared to cordieriteflowthrough filter, our nSiRF-C filters generate back-pressureequivalent to the cordierite flow-through substrate even when they areused in a wall-flow configuration. It can be inferred that sincebackpressure had been a big problem in wall-flow DPTs, as observed inFIG. 31, using wall-flow DPTs made of nSiRF-C materials, as invented inthis patent, leads to an excellent alternative. Additionally it is alsoobserved that a comparison of back-pressures observed with AETB-11substrate/filter versus the AETB-12 and AETB-16 substrates/filtersallows us to infer that increasing the ‘overlap’ channel length leads tobetter back-pressure performance.

FIG. 32 is the same test performed at an operating temperature of 1100Farenheit and the trends in results are almost identical.

Example 5 Preparation of Catalytic and Filtering Substrates

Substrates/filters were prepared as described in Example 2 unlessmentioned explicitly.

AETB-12 was purchased from COI Ceramics and used as the nSiRF-C materialof choice with a density of 12 lbs/ft³. A laser-based channel drillingtechnique was tested to generate holes at 3000 cpsi and 30000 cpsi. Theholes were drilled using a DPSS laser system as describe din this patentand in related prior art elsewhere. The holes generated using a pulsed,high-energy laser system were square in shape and due to the particularconfiguration, presented a high frontal surface area. The presence of ahigh frontal surface area (caused by a large value for wall thickness ofchannels) was obvious in the Delta-P tests carried out using the sametest-flow reactor as described in Example 3. It was observed that forthe early-stage prototype created using laser-based drilling techniquesto be a success, the Delta back-pressure had to be brought to a valueless than 10 inches of water. Further modifications can be done todecrease (or increase) the cell density and to alter the wall thicknessas prescribed by the need of the application.

FIG. 33 shows the change in pressure as a function of N2 gas flow-ratefor the AETB-12 substrate/filter with 30000 cpsi cell density at 27° C.and 400° C. FIG. 34 shows the change in pressure as a function ofoperating temperature for various N₂ gas flow-rates for AETB-12substrate/filter with 30000 cpsi cell density.

FIG. 35 shows the change in pressure as a function of N₂ gas flow-ratefor the AETB-12 substrate/filter with 3000 cpsi cell density at 29° C.and 400° C.

Example 6 Diesel Particulate Filter

The substrate is created using the AETB formulation and formed into abillet having the dimensions of about 13 inches×about 13 inches×about 5inches with a density of about between 8 pounds per cubic foot. From thebillet, a five inch tall cylinder slug which is about six inches indiameter is cut from the billet using a diamond tipped saw. Thissubstrate is further machined to exact tolerances (within 0.001 inches)on a spinning lathe.

Then a plurality of channels are formed in the substrate to form asubstrate containing 600 channels per square inch and having a wall flowconfiguration. The channels are formed using the combined drilling andcomb techniques described herein. The channels are square shape having adimension of about 6 mils by 6 mils. The adjacent walls of adjacentchannels are substantially parallel to each other. The channels do notextend through the entire length of the substrate but are approximately4.9 inches in length.

Example 7 Measurement of Gross Surface Area

The first and second cordierite samples have a gross surface area of33.2 and 46.97 square inches per cubic inch, respectively. Thus, in aone inch cube of the first cordierite sample, there is 33.20 squareinches of surface to put the precious metal loadings. A sample of asubstrate of the present invention has a gross surface area of 83.58square inches per cubic inch.

The gross wall volumes for both the first and second cordierite samplesare 0.311 in³/in³ (cubic inches per cubic inch). The gross wall volumeof the substrate of the present invention is 0.272 cubic inches percubic inch. While this value is less than the first and secondcordierite samples, the present invention has a much higher porosity andpermeability, making the smaller gross wall volume more efficient.

Example 8 Activity Test

An activity test measures the amount of pollutants entering and exitingthe filter. In an activity test, a sample filter is placed in a reactorand gases of a known flow rate and temperature are pumped through thematerial. The activity test then measures the amount of pollutantsexiting the filter. Referring to FIG. 24, an activity test of anexemplary substrate 2410 of the present invention and a sample ofcordierite 2420 is shown. The test measured the activity of toluene at aconcentration of 500 ppm and space velocity of 40,000 per hour. The celldensity of the two samples were both 400 cpsi.

The test illustrates that the substrate 2410 of the present inventionhas a faster light off time and at a significantly lower temperaturethan the cordierite sample 2420. Substrate 2410 achieved 85% destructionat a temperature about 335 degrees Fahrenheit in about three to fourseconds. Cordierite 2420 achieved 85% destruction at about 380 degreesFahrenheit. Substrate 2410 then achieved 90% destruction at about 360degrees Fahrenheit in about four to five seconds. Cordierite 2420achieved 90% destruction at about 450 degrees Fahrenheit in about eightseconds. Substrate 2410 achieved substantially 100% destruction at about425 degrees Fahrenheit in about five seconds. Cordierite 2420 isprojected to achieve substantially 100% destruction at about 800 degreesFahrenheit in about 28 seconds.

Example 9 Permeability of a Catalytic Substrate

The permeability of an exemplary embodiment of Example 2 of the presentinvention is approximately 1093 cd (centidarcies). Other testing valueswere over the maximum number measured by the testing equipment. Incomparison to conventional systems, a sample of cordierite has apermeability of about 268 cd.

Example 10 Testing a Catalytic Converter of Example 2

Similar to an activity test, the EPA utilizes a test known as FederalTest Procedure (“FTP”) 75 that actually mounts the filter on thetailpipe of a car and drives the car under specified conditions. The EPAuses this test for emission certification of vehicles. FTP 75 tests theconditions of the vehicle in three phases. The first phase includescrank and non-idle hold and driving for 505 seconds. This phase reflectsconditions experienced at the beginning of a trip when the engine andthe emission control system begin operation at ambient temperature andare not performing at optimum levels (i.e., the catalyst is cold and hasnot reached the “light off” temperature needed to efficiently controlemissions coming from the engine) until part way through the trip. Thesecond phase includes 864 seconds of driving with a non-idle hold,shutdown, and five extra sampling seconds. This phase reflects thecondition of the engine when the vehicle has been in continuousoperation long enough for all systems to have attained stable operatingtemperatures. The vehicle then has a soak time between 540 seconds and660 seconds. This soak time reflects the condition of an engine that hasbeen turned off and has not cooled to ambient conditions. The thirdphase is a crank and non-idle hold and driving for 505 seconds. Underthese circumstances, the engine and catalyst are warm and, although notat peak operating efficiency when started, still have significantlyimproved emissions performance relative to the cold start mode.

Example 11 Thermal Testing of a Catalytic Substrate

The thermal conductivity of an exemplary embodiment of the presentinvention is approximately 0.0604 W/m-K (Watts of energy per meter thickand Kelvin changed). By comparison, a sample of cordierite is about 1.3to 1.8 W/m-K. These results indicate that, if 1000 Watts of heat energyis lost from a given volume of cordierite material, only 33 Watts wouldbe lost from the same volume of the material from the present invention.Thus, the material of the present invention has a thermal conductivitythirty times greater than cordierite.

The specific heat of an exemplary embodiment of the present invention isapproximately 640 J/kg-K (Joules per kilogram-Kelvin). A sample ofcordierite is about 750 J/kg-K. Even though the cordierite has a greaterspecific heat, cordierite filters have a greater mass to heat up. Theresult is more heat energy is needed to reach operating temperaturemaking the cordierite less efficient.

A multiple use temperature limit is the maximum temperature in which asubstance can be subjected a plurality of times without any degradation.The higher the temperature a substrate can continue to operate withoutmicro-fractures or spallation, the less chance of the substrate breakingor cracking over time. This in turn means the substrate is more durableover a wider temperature range. A higher temperature limit is preferred.

The multiple use temperature limit of an exemplary embodiment of thepresent invention is 2,980 degrees Celsius. A sample of cordierite isabout 1,400 degrees Celsius. Thus, the material of the present inventioncan withstand more than twice the temperature than cordierite beforebreaking down. This permits the material to function in a greater rangeof exhaust environments.

The coefficient of thermal expansion is a ratio of the increase of thelength (linear coefficient), area (superficial), or volume of a body fora given rise in temperature (usually for zero to one degree Celsius) tothe original length, area, or volume, respectively. These threecoefficients are approximately in the ratio 1:2:3. When not specificallyexpressed, the cubical coefficient is usually intended. The less asubstrate will expand when heated, the less chance of leaking,fracturing, or damage to filter assembly. A lower thermal expansion ispreferred to ensure that the substrate keeps its dimensions even whenheated or cooled.

The coefficient of thermal expansion for an exemplary embodiment of thepresent invention is approximately 2.65×10⁻⁷ W/m-K (Watts per meterdegree Kelvin). A sample of cordierite is about 2.5×10⁻⁶/° C. to3.0×10⁻⁶/° C. The thermal expansion of the material of the presentinvention is less than ten times that of cordierite.

The coefficient of thermal expansion of the substrate is preferably, inone embodiment, compatible with the coefficient of thermal expansion ofthe washcoat. If the coefficient of thermal expansion is not similar,the washcoat will spallate, delaminate, “flake” or peel off thesubstrate, resulting in the precious metals being blown away or pluggingthe pore spaces. This would eventually lead to increased backpressure,overheating and system failure.

Example 12 Structural Integrity

The tensile modulus of AETB-12 is approximately 2.21 MPa (mega-Pascal ofpressure which equals approximately 22.1 times the pressure of oneatmosphere of pressure). A sample of cordierite is about 25.0 MPa.Although the cordierite is about ten times stronger, the material of thepresent invention can withstand 22.1 atmospheres of pressure beforerupture. This value is sufficient for uses described herein.

Example 13 Acoustical Testing

Acoustic attenuation may be defined as either the diminution ofthickness, thinness, emaciation; diminution of density; diminution offorce or intensity; or weakening. In one embodiment of the presentinvention, the acoustic attenuation is the substrate's ability toattenuate or dampen acoustic energy in engine exhaust. A substrate ofthe present invention can replace or compliment an engine's mufflerassembly, as disclosed herein, thus decreasing exhaust noise and exhaustsystem costs. A higher acoustic attenuation is preferred.

Currently, there are no accredited laboratory tests that can be appliedto the present invention in any configuration. All American Society forTesting and Materials (“ASTM”) acoustical tests are applied to a largespace such as a sound-proofed room and not a material. However, insimple test using a sound meter, the noise from automobiles was found tobe at least 25 decibels less than conventionally muffled vehicles when asubstrate of the present invention is in the exhaust system. Forreference, 110 decibels is the level that will cause permanent damage tohuman ears, and 60 decibels is the amount of noise in a luxuryautomobile at idle with the windows rolled up.

Example 14 Comparison to Prior Art Substrates

A sample of a suitable nSiRF-C (AETB-12) was compared to cordierite andSiC, measuring a number of attributes.

Silicon Carbide AETB-12 Cordierite (SiC) Thermal 6.04 × 10⁻² W/m-K1.3-1.8 W/m-K 20 W/mK Conductivity Specific Heat 640 J/kg-K 750 J/kg-K950 J/kg-K Density 0.2465 gm/cc 2-2.1 gm/cc 3.2 gm/cc Emissivity 0.88.13 .90 Axial Strength 2.21 Mpa 2.5 Mpa 18.6 Mpa Noise Attenuation 74 db100 db 100 db at 3500 rpm Porosity 97.26% 18-42% 30-40% Permeability1093-∞ cd 268 cd 6.65 cd Regeneration Time 0.75 sec 2 min-20 hrs 50sec-20 hrs Surface Area 88,622 in² 847 in² 847 in² Melting Point 3,000°C. 1,400° C. 2400 Thermal Expansion 0.25 × 10 − 7 1/C. 0.7 × 10 − 6 1/C.4-5 × 10 − 6 1/C. (CTE)

Example 15

In one embodiment, the substrate of the present invention has 600 cpsiwith 6 mil walls. The cell density of a sample substrate of the presentinvention is compared with two samples of cordierite. In comparison, thefirst and second cordierite samples are 100 cpsi with 17 mil wallthickness and 200 cpsi with 12 mil wall thickness, respectively. Incomparison, the substrate of the present invention in this embodimenthas 600 cpsi with 6 mil walls.

In this exemplary embodiment, the substrate is drilled with 0.04 inchdiameter channels spaced every 0.06 inches across the entire filter.These channels are smaller than conventional cordierite channels. Theresult is vastly increased surface area as compared to cordierite, evenwithout taking into consideration the surface area existing in themassive pore space of the substrate material. The channels arepreferably “blind” channels. Exhaust emission is forced to pass throughthe channel walls, rather than flowing in and out of the channelswithout reacting with the catalyst.

The channels are drilled using a CNC drill, which is computer controlledto maintain uniformity. The drilling process is performed under aconstant water shower to prevent dust from becoming airborne, which isan OSHA hazard, and may get into the bearings of the drill and destroyit.

The drilled substrate is oven dried to drive or bake off any water orother liquid that may reside in the pore space before any catalyticapplications. Baking time is not variable and evaporation of the watercan be determined by simply weighing the substrate. Baking timeprimarily speeds up the dewatering process. After heating the filterelement for several different intervals, the weight will level off andthe substrate is ready for any catalyst or coating application.

GLOSSARY

The term “substrate” as used herein refers to a solid surface on whichpollutants can be converted to nonpollutants. A substrate is understoodto include a filter element, catalytic substrate, or filteringsubstrate.

The term “high grade refractory fiber” as used herein refers to.

The term “sintered” as used herein refers to material that has beenheated without melting.

The term “non-woven” as used herein means that there is no interlacingor interweaving pattern of fibers present.

The term “billet” as used herein refers to an unshaped or unmachinedblock of substrate material.

The term “green billet” as used herein refers to a billet that has notbeen cured.

The term “frontal surface” as used herein refers to surface throughwhich the fluid enters the substrate. In certain embodiments, thechannels have openings in the frontal surface and the channels areperpendicular to the frontal surface.

The term “rear surface” as used herein refers to the surface throughwhich the fluid exits the substrate. In certain embodiments, thechannels have openings in the rear surface and the channels areperpendicular to the rear surface.

The term “mil” as used herein refers to a unit of measurement and isequivalent to a thousandth of an inch.

The term “light off temperature” as used herein refers to thetemperature at which conversion of the reaction in catalytic converteris 50%. That is, the light off temperature is the temperature at which50% of one or more pollutants, or alternatively total pollutants, areconverted into nonpollutants.

The term “burn off” as used herein refers to a process of combustingparticulate matter and other material that is filtered by a substrate.For example, burn off may occur in a diesel particulate filter (DPF).

The term “channel” as used herein refers to a three-dimensional openingin the substrate that extends through at least a portion of thesubstrate and has a definitive shape and length.

The term “channels per square inch” as used herein refers to the numberof channels present in a cross-sectional square inch of the substrate.The term cells per square inch is synonymous.

The term “channel shape” as used herein refers to the three-dimensionalshape of the channel.

The term “PM” as used herein refers to particulate matter. Commonmeasurements of PM include PM-10 and PM-2.5.

The term “gross surface area” as used herein is the total surface areaand represents the total surface area that precious metals can beimpregnated onto in one cubic inch.

The term “2-way catalytic converter” as used herein refers to acatalytic converter that only oxidizes the gas-phase pollution of HC andCO to CO₂ and H₂O.

The term “3-way catalytic converter” as used herein refers to acatalytic converter that oxidizes CO and HC to CO₂ and H₂O and alsoreduces NO_(x) to N₂.

The term “4-way catalytic converter” as used herein refers to acatalytic converter that performs the oxidation and reduction asdescribed for a 3-way catalytic converter but also traps particulates toburn them off (regeneration can occur in active or passive mode).

The term “suitable for use” as used herein refers meeting therequirements of particular regulatory guidelines.

The term “thermal conductivity” as used herein refers to the quantity ofheat that passes in unit time through unit area of a plate of a givenmaterial, when its opposite faces are subject to unit temperaturegradient (e.g., one degree temperature difference across a thickness ofone unit).

The term “matting” as used herein generally refers to any material thatis used to provide insulation and/or protection to a substrate. Mattingis sometimes also referred to as batting.

The term “boron binder” as used herein refers to an agent present in anSiRF-C after the sintering process and that is derived from a boronbiding agent.

The term “pecking” as used herein refers to a process of forming orreshaping a channel in a substrate by way of repeatedly forcing a tineinto and out of a substrate material until the desired length of thechannel is obtained.

Having now fully described this invention, it will be understood bythose of ordinary skill in the art that the same can be performed withina wide and equivalent range of conditions, formulations and otherparameters without affecting the scope of the invention or anyembodiment thereof. All patents and publications cited herein are fullyincorporated by reference herein in their entirety.

1. A method of forming a porous substrate comprising: mixing ceramicfibers with a liquid to form a formable mixture; adding a catalyst;forming a green substrate; sintering the green substrate to form a rigidcomposite fibrous structure having fibers arranged in a non-woventhree-dimensional matrix having pore space occupying at least 60% of thevolume within the fibrous structure, the sintering step formingfiber-to-fiber bonds in the rigid composite fibrous structure, the rigidcomposite fibrous structure having a honeycomb arrangement of channels;and wherein step of adding a catalyst is preformed before the sinteringstep.
 2. The method according to claim 1 wherein the step of adding acatalyst is preformed before the forming step.
 3. The method accordingto claim 1 wherein the step of adding a catalyst is performed during themixing step.
 4. The method according to claim 3 wherein the catalyst ismixed with the fibers and liquid.
 5. The method according to claim 3wherein the catalyst is added to the liquid.
 6. The method according toclaim 1 wherein the catalyst is in the form of a liquid.
 7. The methodaccording to claim 1 wherein the catalyst adheres to the fibers duringsintering.
 8. The method according to claim 1 wherein the catalyst islocated within the pore space in the three-dimensional matrix.
 9. Themethod according to claim 1 further comprising forming channels, andwherein the catalyst located in the channels.
 10. The method accordingto claim 1 wherein the catalyst is at least one of palladium, platinum,rhodium, chromium, nickel, rhenium, ruthenium, silver, osmium, iridium,vanadium, gold, iridium and magnesium.
 11. The method according to claim1 wherein the catalyst is organic.
 12. The method according to claim 1wherein the catalyst is at least one of a non-metallic catalyst, a rareearth catalyst, a base metal catalyst, a precious metal catalyst and anoble metal catalyst.
 13. The method according to claim 1 wherein thecatalyst comprises at least one of an oxidation catalyst, a reductioncatalyst, a two-way catalyst, a three-way catalyst, a four-way catalyst,a NOx adsorber, and mixtures thereof.
 14. The method according to claim1 wherein the catalyst is suitable for catalyzing an oxidation reactionof a hydrocarbon.
 15. The substrate according to claim 1, wherein thecatalyst is added in an amount of about 5 to about 150 grams per cubicfoot in the rigid composite fibrous structure.